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Chiral Brønsted Acid Catalyzed Enantioselective Allenylation of Aldehydes Leleti Rajender Reddy,* Chemical and Analytical Development, Novartis Pharmaceutical Corporation, East Hanover, New Jersey 07936, USA General Information. All the reactions were performed under nitrogen gas in glassware’s (screw-cap test tubes) that was flame-dried and equipped with a magnetic stirring bar. Thin- layer chromatography (TLC) was performed using silica gel 60 F254 pre-coated plates (0.25 mm). Flash chromatography was performed using silica gel (40 μm particle size). All compounds were judged pure by TLC analysis (single spot/ two solvent systems) using a UV lamp or PMA for detection purposes. 1 H and 13 C NMR spectra were recorded on a FT-NMR spectrometer at 500 and 125 MHz, respectively. High-resolution mass spectroscopy (HRMS) was carried out in electro spray mode. Enantiomeric excess (ee) was determined using a Waters HPLC a 996 photodiode array detector. The (R)-TRIP-PA (4) was purchased from Aldrich. All solvents were purchased from Aldrich and used without further purification. The propargyl borolane (2) was prepared according to literature procedures. 1 General procedure for the asymmetric propargylation of aldehydes (GP1): Unless indicated otherwise, the reaction temperatures refer to external reaction temperatures. All the compounds were known compounds and were characterized by comparing their 1 H NMR and 13 C NMR values to the reported values. A screw-cap reaction tube with a stir bar was evacuated, flame-dried, and back-filled with nitrogen. To this tube was added the (R)-TRIP-PA catalyst 4 (5 mol %), aldehyde 1 (1.0 mmol) and cyclohexane (10.0 mL). The reaction mixture was then cooled to 0 °C followed by the addition of propargyl borolane 2 (1.2 mmol), drop wise (10 min). The mixture was stirred at this temperature 12 h. The reaction mixture was washed with saturated NaHSO 3 solution (10 mL) and water (10 mL) and purified by flash chromatography using ethyl acetate and heptanes (2: 8). The pure silyl alcohol was dissolved in THF (5 mL) and was added commercially available tetrabutylammonium fluoride (2 mL, 2.0 mmol, 1.0 M solution in THF, dried over 4 Å molecular sieves for 48 h) at 78 °C. After stirring the reaction mixture for 4 h at −78 °C , it was quenched Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2012

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Chiral Brønsted Acid Catalyzed Enantioselective Allenylation of Aldehydes

Leleti Rajender Reddy,*

Chemical and Analytical Development, Novartis Pharmaceutical Corporation, East Hanover, New Jersey 07936, USA

General Information. All the reactions were performed under nitrogen gas in glassware’s

(screw-cap test tubes) that was flame-dried and equipped with a magnetic stirring bar. Thin-

layer chromatography (TLC) was performed using silica gel 60 F254 pre-coated plates (0.25

mm). Flash chromatography was performed using silica gel (40 μm particle size). All compounds

were judged pure by TLC analysis (single spot/ two solvent systems) using a UV lamp or PMA for

detection purposes. 1H and 13C NMR spectra were recorded on a FT-NMR spectrometer at 500

and 125 MHz, respectively. High-resolution mass spectroscopy (HRMS) was carried out in

electro spray mode. Enantiomeric excess (ee) was determined using a Waters HPLC a 996

photodiode array detector. The (R)-TRIP-PA (4) was purchased from Aldrich. All solvents were

purchased from Aldrich and used without further purification. The propargyl borolane (2) was

prepared according to literature procedures.1

General procedure for the asymmetric propargylation of aldehydes (GP1):

Unless indicated otherwise, the reaction

temperatures refer to external reaction temperatures. All the compounds were known

compounds and were characterized by comparing their 1H NMR and 13C NMR values to the

reported values.

A screw-cap reaction tube with a stir bar was evacuated, flame-dried, and back-filled with

nitrogen. To this tube was added the (R)-TRIP-PA catalyst 4 (5 mol %), aldehyde 1 (1.0 mmol)

and cyclohexane (10.0 mL). The reaction mixture was then cooled to 0 °C followed by the

addition of propargyl borolane 2 (1.2 mmol), drop wise (10 min). The mixture was stirred at this

temperature 12 h. The reaction mixture was washed with saturated NaHSO3 solution (10 mL)

and water (10 mL) and purified by flash chromatography using ethyl acetate and heptanes (2:

8). The pure silyl alcohol was dissolved in THF (5 mL) and was added commercially available

tetrabutylammonium fluoride (2 mL, 2.0 mmol, 1.0 M solution in THF, dried over 4 Å molecular

sieves for 48 h) at −78 °C. After stirring the reaction mixture for 4 h at −78 °C , it was quenched

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with saturated NaCl solution (10mL) at the same temperature and the reaction mixture was

allowed to room temperature. The reaction mixture was extracted with ethyl acetate (2 X 10

mL). The combined organic layers was washed with water (10 mL) and concentrated to dryness

to obtain crude product. This was purified by flash chromatography using ethyl acetate and

heptanes (2: 8) to obtain pure alcohol 3.

General procedure for the asymmetric propargylation of aldehydes (GP2):

A screw-cap reaction tube with a stir bar was evacuated, flame-dried, and back-filled with

nitrogen. To this tube was added the (R)-TRIP-PA catalyst 4 (5 mol %), aldehyde 1 (1.0 mmol)

and cyclohexane (10.0 mL). The reaction mixture was then cooled to 0 °C followed by the

addition of propargyl borolane 2 (1.2 mmol), drop wise (10 min). The mixture was stirred at this

temperature 12 h. After comlition of the reaction, it was diluted with THF (5 mL) and was

added commercially available tetrabutylammonium fluoride (2 mL, 2.0 mmol, 1.0 M solution in

THF, dried over 4 Å molecular sieves for 48 h) at −78 °C. After stirring the reaction mixture for 4

h at −78 °C, it was quenched with saturated NaCl solution (10mL) at the same temperature and

the reaction mixture was allowed to room temperature. The reaction mixture was extracted

with ethyl acetate (2 X 10 mL). The combined organic layers was washed with water (10 mL)

and concentrated to dryness to obtain crude product. This was purified by flash

chromatography using ethyl acetate and heptanes (2: 8) to obtain pure alcohol 3.

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(R)-1-(4-chlorophenyl)buta-2,3-dien-1-ol (3a):

Following the general procedure (GP1), the reaction of adehyde 1a (140 mg, 1.0 mmol) with

boronate 2 (285 mg, 1.2 mmol) afforded alcohol 3a as viscous oil (170 mg, 94%) with 95% ee.

Enantiomeric excess was determined by HPLC with a Chiralcel OD-H column equipped with an

OD-H guard column (2% IPA in hexane, flow rate = 0.8 mL/min), tmajor = 25.03 min, tminor = 26.40

min. [α]20D = −56.2 (c 0.8, CHCl3), [literature2

Following the general procedure (GP2), the reaction of adehyde 1a (141 mg, 1.0 mmol) with

boronate 2 (286 mg, 1.2 mmol) afforded alcohol 3a as viscous oil (160 mg, 88%) with 95% ee.

for R-enantiomer with 76% ee. [α]20D = –45.2 (c

1.0, CHCl3)]. 1H NMR (400 MHz, CDCl3) δ ppm 7.32 (s, 4 H), 5.39 (q, J=6.48 Hz, 1 H), 5.23 (dd,

J=4.17, 2.40 Hz, 1 H), 4.86 - 5.00 (m, 2 H), 2.34 (s, 1 H). 13C NMR (125 MHz, CDCl3) δ ppm 207.1,

141.2, 133.4, 128.6, 127.5, 94.9, 78.4, 71.3.

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(R)-1-(4-bromophenyl)buta-2,3-dien-1-ol (3b):

Following the general procedure (GP1), the reaction of adehyde 1b (185 mg, 1.0 mmol) with

boronate 2 (285 mg, 1.2 mmol) afforded alcohol 3b as viscous oil (200 mg, 90%) with 95% ee.

Enantiomeric excess was determined by HPLC with a Chiralcel OD-H column equipped with an

OD-H guard column (2% IPA in hexane, flow rate = 0.8 mL/min), tmajor = 20.88 min, tminor = 23.35

min. [α]20D = −52.2 (c 1.1, CHCl3). 1H NMR (400 MHz, CDCl3) δ ppm 7.26 - 7.37 (m, 2 H), 7.11 (d,

J=8.34 Hz, 2 H), 5.23 (q, J=6.57 Hz, 1 H), 5.01 - 5.09 (m, 1 H), 4.68 - 4.84 (m, 2 H), 2.30 (br. s., 1

H). 13C NMR (125 MHz, CDCl3) δ ppm 206.9, 141.5, 131.2, 127.6, 121.3, 94.6, 78.2, 71.1.

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(R)-1-phenylbuta-2,3-dien-1-ol (3c):

Following the general procedure (GP1), the reaction of adehyde 1c (108 mg, 1.0 mmol) with

boronate 2 (285 mg, 1.2 mmol) afforded alcohol 3c as viscous oil (132 mg, 93%) with 91% ee.

Enantiomeric excess was determined by HPLC with a Chiralcel OJ-H column equipped with an

OJ-H guard column (3% IPA in hexane, flow rate = 0.8 mL/min), tmajor = 34.22 min, tminor = 46.19

min. [α]20D = −33.2 (c 1.0, CHCl3). [literature3

for R-enantiomer with 99% ee. [α]20D = –34.1 (c

1.2, CHCl3)]. 1H NMR (400 MHz, CDCl3) δ ppm 7.15 - 7.45 (m, 5 H), 5.44 (q, J=6.57 Hz, 1 H), 5.26

(d, J=6.32 Hz, 1 H), 4.83 - 5.01 (m, 2 H), 2.25 (s, 1 H). 13C NMR (125 MHz, CDCl3) δ ppm 207.1,

142.8, 128.5, 127.8, 126.1, 95.2, 78.2, 72.0.

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(R)-1-(o-tolyl)buta-2,3-dien-1-ol (3d):

Following the general procedure (GP1), the reaction of adehyde 1d (120 mg, 1.0 mmol) with

boronate 2 (285 mg, 1.2 mmol) afforded alcohol 3d as viscous oil (144 mg, 90%) with 91% ee.

Enantiomeric excess was determined by HPLC with a Chiralcel OD-H column equipped with an

OD-H guard column (2.5% IPA in hexane, flow rate = 0.8 mL/min), tmajor = 13.42 min, tminor =

15.85 min. (The silyl intermediate was isolated 202 mg, 92% yield). [α]20D = −46.2 (c 1.3,

CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.28 - 7.39 (m, 1 H), 6.93 - 7.15 (m, 3 H), 5.31 - 5.38 (m, 1

H), 5.25 (q, J=6.48 Hz, 1 H), 4.64 - 4.82 (m, 2 H), 2.21 (s, 3 H). 13C NMR (125 MHz, CDCl3) δ ppm

207.0, 140.5, 134.9, 130.2, 127.3, 126.0, 125.1, 94.1, 77.7, 68.8, 24.4, 18.8.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

(R)-1-(p-tolyl)buta-2,3-dien-1-ol (3e):

Following the general procedure (GP1), the reaction of adehyde 1e (120 mg, 1.0 mmol) with

boronate 2 (285 mg, 1.2 mmol) afforded alcohol 3e as viscous oil (148 mg, 93%) with 91% ee.

Enantiomeric excess was determined by HPLC with a Chiralcel OD-H column equipped with an

OD-H guard column (5% IPA in hexane, flow rate = 0.8 mL/min), tmajor = 17.34 min, tminor = 21.32

min. [α]20D = −52.5 (c 0.9, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.28 (d, J=8.08 Hz, 2 H), 7.16 (d,

J=7.83 Hz, 2 H), 5.42 (q, J=6.57 Hz, 1 H), 5.18 - 5.29 (m, 1 H), 4.84 - 4.98 (m, 2 H), 2.34 (s, 3 H),

2.13 (br. s., 1 H). 13C NMR (125 MHz, CDCl3) δ ppm 207.1, 139.9, 137.5, 129.2, 126.0, 95.2, 78.1,

71.8, 21.1.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

(R)-1-(p-Methoxyphenyl)buta-2,3-dien-1-ol (3f):

Following the general procedure (GP1), the reaction of adehyde 1f (136 mg, 1.0 mmol) with

boronate 2 (285 mg, 1.2 mmol) afforded alcohol 3f as viscous oil (163 mg, 93%) with 90% ee.

Enantiomeric excess was determined by HPLC with a Chiralcel OD-H column equipped with an

OD-H guard column (2.5% IPA in hexane, flow rate = 0.8 mL/min), tmajor = 18.93 min, tminor =

26.87 min. [α]20D = −53.1 (c 0.8, CHCl3). 1H NMR (400 MHz, CDCl3) δ 77.24 - 7.39 (m, 2 H), 6.85

- 6.96 (m, 2 H), 5.21 (t, J=2.91 Hz, 1 H), 4.71 (dd, J=4.93, 3.16 Hz, 2 H), 3.75 - 3.89 (m, 4 H), 1.91

(s, 1 H). 13C NMR (125 MHz, CDCl3) δ ppm 207.8, 160.4, 136.3, 129.4, 114.7, 102.6, 85.1, 74.1,

73.4, 56.4, 25.8.

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(R)-1-(thiophen-2-yl)buta-2,3-dien-1-ol (3g):

Following the general procedure (GP1), the reaction of adehyde 1g (112 mg, 1.0 mmol) with

boronate 2 (285 mg, 1.2 mmol) afforded alcohol 3g as viscous oil (135 mg, 89%) with 95% ee.

Enantiomeric excess was determined by HPLC with a Chiralcel OD-H column equipped with an

OD-H guard column (5% IPA in hexane, flow rate = 0.8 mL/min), tmajor = 11.93 min, tminor = 14.34

min. [α]20D = −42.3 (c 1.2, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.10 - 7.18 (m, 1 H), 6.77 - 6.95

(m, 2 H), 5.26 - 5.50 (m, 2 H), 4.70 - 4.94 (m, 2 H), 2.27 (d, J=3.79 Hz, 11 H). 13C NMR (125 MHz,

CDCl3) δ ppm 207.1, 146.9, 126.7, 125.2, 124.3, 94.8, 78.8, 68.0.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

(S,E)-1-phenylhexa-1,4,5-trien-3-ol (3h):4

Following the general procedure (GP1), the reaction of adehyde 1h (132 mg, 1.0 mmol) with

boronate 2 (285 mg, 1.2 mmol) afforded alcohol 3h as viscous oil (158 mg, 92%) with 82% ee.

Enantiomeric excess was determined by HPLC with a Chiralcel OD-H column equipped with an

OD-H guard column (5% IPA in hexane, flow rate = 0.8 mL/min), tmajor = 20.13 min, tminor = 30.79

min. [α]20D = +51.5 (c 0.6, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.35 - 7.42 (m, 2 H), 7.27 - 7.35

(m, 2 H), 7.19 - 7.27 (m, 1 H), 6.63 (d, J=15.66 Hz, 1 H), 6.27 (dd, J=15.92, 6.32 Hz, 1 H), 5.36 (q,

J=6.32 Hz, 1 H), 4.92 (dd, J=6.57, 2.53 Hz, 2 H), 4.80 - 4.89 (m, 1 H), 2.13 (br. s., 1 H). 13C NMR

(125 MHz, CDCl3) δ ppm 207.3, 136.5, 130.7, 130.4, 128.6, 127.8, 126.6, 98.8, 78.2, 70.4.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

(S)-1-phenylhexa-4,5-dien-3-ol (3i):

Following the general procedure (GP1), the reaction of adehyde 1i (134 mg, 1.0 mmol) with

boronate 2 (285 mg, 1.2 mmol) afforded alcohol 3i as viscous oil (156 mg, 90%) with 96% ee.

Enantiomeric excess was determined by HPLC with a Chiralcel OD-H column equipped with an

OD-H guard column (8% IPA in hexane, flow rate = 0.8 mL/min), tmajor = 12.24 min, tminor = 14.29

min. [α]20D = +14.3 (c 1.1, CHCl3). [literature4

for S-enantiomer with 88% ee. [α]20D = +11.8 (c

1.0, CHCl3)]. 1H NMR (400 MHz, CDCl3) δ 7.09 - 7.37 (m, 5 H), 5.28 (q, J=6.57 Hz, 1 H), 4.88 (dd,

J=6.69, 2.40 Hz, 2 H), 4.12 - 4.25 (m, 1 H), 2.61 - 2.86 (m, 2 H), 1.82 - 2.00 (m, 2 H), 1.71 (br. s., 1

H). 13C NMR (125 MHz, CDCl3) δ ppm 207.0, 141.8, 128.4, 125.8, 94.7, 77.8, 68.9, 39.0, 31.7.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

(S)-1-cyclohexylbuta-2,3-dien-1-ol (3j):

Following the general procedure (GP1), the reaction of adehyde 1j (112 mg, 1.0 mmol) with

boronate 2 (285 mg, 1.2 mmol) afforded alcohol 3j as viscous oil (142 mg, 94%) with 99% ee.

Enantiomeric excess was determined by HPLC with a Chiralcel OJ-H column equipped with an

OJ-H guard column (1% IPA in hexane, flow rate = 0.8 mL/min), tmajor = 15.71 min, tminor = 13.59

min. [α]20D = +16.8 (c 1.0, Benzene). [literature4 for S-enantiomer with 90% ee. [α]20

D = +14.2

(c 1.1, Benzene)]. 1H NMR (400 MHz, CDCl3) δ 5.09 (q, J=6.57 Hz, 1 H), 4.71 (dd, J=6.57, 2.27 Hz,

2 H), 3.72 - 3.86 (m, 1 H), 1.46 - 1.79 (m, 6 H), 1.23 - 1.40 (m, 1 H), 0.77 - 1.23 (m, 5 H). 13C NMR

(125 MHz, CDCl3) δ ppm 207.0, 93.0, 73.8, 43.9, 28.4, 28.0, 26.2, 25.8, 25.8, 24.4.

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1 R. W.Hoffmann, H. Brinkmann, G. Frenking, Chemische Berichte 1990, 123, 2387. 2 Y. Wang, K. Zheng, R. Hong. J. Am. Chem. Soc. 2012, 134, 4096.

3 M. Yoshida, Y. Shoji, K. Shishido. Tetrahedron 2010, 66, 5053.

3 E. J. Corey, M. L. Chan, H. Duck. J. Am. Chem. Soc. 1990, 112, 878.

4 G. Xia, H. Yamamoto. J. Am. Chem. Soc. 2007, 129, 496.

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5/16/2012 3:54:14 PM

Acquisition Time (sec) 3.9584 Comment Chloro-allenyl-p Date 18 Apr 2012 23:10:56Date Stamp 18 Apr 2012 23:10:56File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Chloro-allenyl-p_010001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 16 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 128.00SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2455.5339Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.32 (s, 4 H), 5.39 (q, J=6.48 Hz, 1 H), 5.23 (dd, J=4.17, 2.40 Hz, 1 H), 4.86 - 5.00 (m, 2 H), 2.34 (s, 1 H)

VerticalScaleFactor = 1Chloro-allenyl-p_010001r

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alize

d In

tens

ity

1.002.021.034.13

M01(s)

M05(s)

M03(dd)

M02(q) M04(m)

2.344.914.

924.

924.

934.93

4.94

5.225.24

5.38

5.40

5.41

7.32

OH

Cl

.

5/16/2012 3:57:46 PM

Acquisition Time (sec) 1.3664 Comment Chloro-allenyl-p Date 19 Apr 2012 05:41:20Date Stamp 19 Apr 2012 05:41:20File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Chloro-allenyl-p_013001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 2048 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 14596.50SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 10062.3271Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1Chloro-allenyl-p_013001r

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Norm

alize

d In

tens

ity

71.3

577

.07

77.3

978.4

994.9

7

127.

5312

8.62

133.

49141.

26

207.

16

OH

Cl

.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 4:26:29 PM

Acquisition Time (sec) 3.9584 Comment P-Br-all-2 Date 06 May 2012 00:00:00Date Stamp 06 May 2012 00:00:00File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\P-Br-all-2_010001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 16 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 90.50SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2400.6772Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.26 - 7.37 (m, 2 H), 7.11 (d, J=8.34 Hz, 2 H), 5.23 (q, J=6.57 Hz, 1 H), 5.01 - 5.09 (m, 1 H), 4.68 - 4.84 (m, 2 H), 2.30 (br. s., 1 H)

VerticalScaleFactor = 1P-Br-all-2_010001r

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alize

d Inte

nsity

1.032.020.992.07

M04(m)

M01(m)

M03(q)

M02(d)

M05(m)

M06(br. s.)

1.13

2.30

4.76

4.76

4.77

4.78

4.79

5.05

5.055.0

75.0

85.2

15.2

35.2

45.2

6

7.10

7.12

7.31

7.31

7.33

7.34

OH

Br

.

5/16/2012 4:29:03 PM

Acquisition Time (sec) 1.3664 Comment P-Br-all-2 Date 06 May 2012 01:16:48Date Stamp 06 May 2012 01:16:48File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\P-Br-all-2_012001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 2048 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 8192.00SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 10035.1045Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1P-Br-all-2_012001r

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Norm

alize

d Inte

nsity

71.13

76.83

77.15

78.20

94.62

121.3

6

127.6

013

1.29

141.5

2

206.9

3

OH

Br

.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 3:54:14 PM

Acquisition Time (sec) 3.9584 Comment Chloro-allenyl-p Date 18 Apr 2012 23:10:56Date Stamp 18 Apr 2012 23:10:56File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Chloro-allenyl-p_010001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 16 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 128.00SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2455.5339Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.32 (s, 4 H), 5.39 (q, J=6.48 Hz, 1 H), 5.23 (dd, J=4.17, 2.40 Hz, 1 H), 4.86 - 5.00 (m, 2 H), 2.34 (s, 1 H)

VerticalScaleFactor = 1Chloro-allenyl-p_010001r

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alize

d In

tens

ity

1.002.021.034.13

M01(s)

M05(s)

M03(dd)

M02(q) M04(m)

2.344.914.

924.

924.

934.93

4.94

5.225.24

5.38

5.40

5.41

7.32

OH

Cl

.

5/16/2012 3:57:46 PM

Acquisition Time (sec) 1.3664 Comment Chloro-allenyl-p Date 19 Apr 2012 05:41:20Date Stamp 19 Apr 2012 05:41:20File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Chloro-allenyl-p_013001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 2048 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 14596.50SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 10062.3271Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1Chloro-allenyl-p_013001r

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Norm

alize

d In

tens

ity

71.3

577

.07

77.3

978.4

994.9

7

127.

5312

8.62

133.

49141.

26

207.

16

OH

Cl

.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 4:26:29 PM

Acquisition Time (sec) 3.9584 Comment P-Br-all-2 Date 06 May 2012 00:00:00Date Stamp 06 May 2012 00:00:00File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\P-Br-all-2_010001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 16 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 90.50SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2400.6772Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.26 - 7.37 (m, 2 H), 7.11 (d, J=8.34 Hz, 2 H), 5.23 (q, J=6.57 Hz, 1 H), 5.01 - 5.09 (m, 1 H), 4.68 - 4.84 (m, 2 H), 2.30 (br. s., 1 H)

VerticalScaleFactor = 1P-Br-all-2_010001r

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alize

d Inte

nsity

1.032.020.992.07

M04(m)

M01(m)

M03(q)

M02(d)

M05(m)

M06(br. s.)

1.13

2.30

4.76

4.76

4.77

4.78

4.79

5.05

5.055.0

75.0

85.2

15.2

35.2

45.2

6

7.10

7.12

7.31

7.31

7.33

7.34

OH

Br

.

5/16/2012 4:29:03 PM

Acquisition Time (sec) 1.3664 Comment P-Br-all-2 Date 06 May 2012 01:16:48Date Stamp 06 May 2012 01:16:48File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\P-Br-all-2_012001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 2048 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 8192.00SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 10035.1045Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1P-Br-all-2_012001r

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Norm

alize

d Inte

nsity

71.13

76.83

77.15

78.20

94.62

121.3

6

127.6

013

1.29

141.5

2

206.9

3

OH

Br

.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 5:12:54 PM

Acquisition Time (sec) 3.9584 Comment Ph-allenyl-1 Date 23 Apr 2012 18:52:48Date Stamp 23 Apr 2012 18:52:48File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Ph-allenyl-1_010001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 16 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 128.00SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2451.4324Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.15 - 7.45 (m, 5 H), 5.44 (q, J=6.57 Hz, 1 H), 5.26 (d, J=6.32 Hz, 1 H), 4.83 - 5.01 (m, 2 H), 2.25 (s, 1 H)

VerticalScaleFactor = 1Ph-allenyl-1_010001r

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)

0

0.5

1.0

1.5

2.0

2.5

3.0

Norm

alize

d Inte

nsity

0.962.000.995.13

M03(d)

M02(q)

M05(s)

M04(m)

M01(m)

2.254.9

14.9

24.93

4.94

5.26

5.275.4

15.4

35.4

55.4

6

7.24

7.29

7.307.3

47.3

57.3

67.39

7.40

7.41

OH.

5/16/2012 5:15:21 PM

Acquisition Time (sec) 1.3664 Comment Ph-allenyl-1 Date 24 Apr 2012 05:41:20Date Stamp 24 Apr 2012 05:41:20File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Ph-allenyl-1_013001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 2048 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 8192.00SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 10062.3271Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1Ph-allenyl-1_013001r

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Norm

alize

d Inte

nsity

72.00

76.76

77.08

77.40

78.27

95.23

126.1

312

8.54

142.8

6

207.1

3

OH.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 5:36:23 PM

Acquisition Time (sec) 3.9584 Comment OMe-allenyl-1 Date 04 May 2012 23:47:12Date Stamp 04 May 2012 23:47:12File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\OMe-allenyl-1_010001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 16 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 128.00SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2396.3875Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.28 - 7.39 (m, 1 H), 6.93 - 7.15 (m, 3 H), 5.31 - 5.38 (m, 1 H), 5.25 (q, J=6.48 Hz, 1 H), 4.64 - 4.82 (m, 2 H), 2.21 (s, 3 H)

VerticalScaleFactor = 1OMe-allenyl-1_010001r

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alize

d Inte

nsity

1.153.012.010.983.321.00

M03(m)

M06(s)

M04(q)

M01(m)M05(m)

M02(m)

1.75

1.75

1.97

2.21

2.284.7

44.7

54.75

4.76

4.77

4.78

5.23

5.24

5.26

5.32

5.34

7.00

7.01

7.05

7.05

7.07

7.09

7.09

7.117.34

7.36

7.36

OH.

Me

5/16/2012 5:39:29 PM

Acquisition Time (sec) 1.3664 Comment OMe-allenyl-1 Date 05 May 2012 00:23:28Date Stamp 05 May 2012 00:23:28File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\OMe-allenyl-1_011001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 256 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 8192.00SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 11042.7217Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1OMe-allenyl-1_011001r

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alize

d In

tens

ity 18.8

9

24.4

2

68.8

3

76.5

176

.8277.1

477

.76

94.1

3

125.

1712

6.00

127.

36130.

24

134.

90

140.

51

207.

09

OH.

Me

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 5:58:55 PM

Acquisition Time (sec) 3.9584 Comment 0-Methyl-all-2 Date 05 May 2012 23:15:12Date Stamp 05 May 2012 23:15:12File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\0-Methyl-all-2_010001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 16 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 101.60SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2449.8203Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.28 (d, J=8.08 Hz, 2 H), 7.16 (d, J=7.83 Hz, 2 H), 5.42 (q, J=6.57 Hz, 1 H), 5.18 - 5.29 (m, 1 H), 4.84 - 4.98 (m, 2 H), 2.34 (s, 3 H), 2.13 (br. s., 1 H)

VerticalScaleFactor = 10-Methyl-all-2_010001r

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alize

d In

tens

ity

1.073.122.021.011.002.01

M01(d)

M02(d)

M06(s)

M04(m)

M05(m)M03(q)

M07(br. s.)

2.13

2.34

4.90

4.904.92

4.93

5.22

5.235.

235.

405.

425.

435.

45

7.15

7.17

7.27

7.29

OH.

Me

5/16/2012 6:02:02 PM

Acquisition Time (sec) 1.3664 Comment 0-Methyl-all-2 Date 06 May 2012 02:40:00Date Stamp 06 May 2012 02:40:00File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\0-Methyl-all-2_012001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 2048 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 13004.00SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 10062.3271Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 10-Methyl-all-2_012001r

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Norm

alize

d Inte

nsity

21.18

71.85

76.77

77.09

77.40

78.1795

.29

126.0

912

9.22

137.5

913

9.98

207.1

0

OH.

Me

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 6:30:09 PM

Acquisition Time (sec) 3.9584 Comment P-OMe-all-2 Date 05 May 2012 23:28:00Date Stamp 05 May 2012 23:28:00File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\p-OMe-all-2_010001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 16 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 181.00SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2471.1260Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.24 - 7.39 (m, 2 H), 6.85 - 6.96 (m, 2 H), 5.21 (t, J=2.91 Hz, 1 H), 4.71 (dd, J=4.93, 3.16 Hz, 2 H), 3.75 - 3.89 (m, 4 H), 1.91 (s, 1 H)

VerticalScaleFactor = 1p-OMe-all-2_010001r

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alize

d In

tens

ity

0.843.662.061.002.402.73

M04(dd)M02(m)

M03(t)M06(s)

M05(m)

M01(m)

1.91

3.84

3.844.

704.71

4.71

4.72

5.205.

215.

21

6.886.91

7.29

7.30

7.32

OH.

OMe

5/16/2012 6:33:26 PM

Acquisition Time (sec) 1.3664 Comment P-OMe-all-2 Date 06 May 2012 14:15:28Date Stamp 06 May 2012 14:15:28File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\p-OMe-all-2_013001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 20000 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 8192.00SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 10176.9072Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1p-OMe-all-2_013001r

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Norm

alize

d In

tens

ity

25.8

156.4

1

73.4

174

.19

77.8

678

.18

78.4

9

85.1

8

102.

67

114.

79

129.

49

136.

37

160.

40

207.

82

OH.

OMe

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 7:50:12 PM

Acquisition Time (sec) 3.9584 Comment Thio-all-2 Date 07 May 2012 02:05:52Date Stamp 07 May 2012 02:05:52File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Thio-all-2_012001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 1024 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 128.00SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2399.9490Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.10 - 7.18 (m, 1 H), 6.77 - 6.95 (m, 2 H), 5.26 - 5.50 (m, 2 H), 4.70 - 4.94 (m, 2 H), 2.27 (d, J=3.79 Hz, 11 H)

VerticalScaleFactor = 1Thio-all-2_012001r

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)

0

0.5

1.0

1.5

2.0

2.5

3.0

Norm

alize

d Inte

nsity

0.952.001.951.971.06

M01(m)

M05(d)

M02(m) M04(m)

M03(m)

2.27

2.28

4.82

4.834.8

4

5.36

5.37

5.39

5.40

5.42

6.82

6.836.8

56.8

86.8

97.1

27.1

27.13

7.14

7.14

OH.

S

5/16/2012 7:52:22 PM

Acquisition Time (sec) 1.3664 Comment Thio-all-2 Date 07 May 2012 03:14:08Date Stamp 07 May 2012 03:14:08File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Thio-all-2_013001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 2048 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 8192.00SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 10062.3271Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1Thio-all-2_013001r

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Norm

alize

d Inte

nsity

68.06

76.7777.09

77.40

78.81

94.8012

4.38

125.2

912

6.76

146.9

3207.1

9

OH.

S

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 10:31:21 PM

Acquisition Time (sec) 3.9584 Comment Cinnamyl-allenyl-1 Date 25 Apr 2012 05:41:20Date Stamp 25 Apr 2012 05:41:20File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Cinnamyl-allenyl-1_013001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 1024 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 114.00SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2450.5845Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.35 - 7.42 (m, 2 H), 7.27 - 7.35 (m, 2 H), 7.19 - 7.27 (m, 1 H), 6.63 (d, J=15.66 Hz, 1 H), 6.27 (dd, J=15.92, 6.32 Hz, 1 H), 5.36 (q, J=6.32 Hz, 1 H), 4.92 (dd, J=6.57, 2.53 Hz, 2 H), 4.80 - 4.89 (m, 1 H), 2.13 (br. s., 1 H)

VerticalScaleFactor = 1Cinnamyl-allenyl-1_013001r

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

1.9

Nor

mal

ized

Inte

nsity

0.911.000.871.011.000.95

M07(dd)

M01(m)

M02(m)

M03(m)

M04(d)

M08(m)

M06(q)

M05(dd)

M09(br. s.)

2.134.

854.85

4.86

4.86

4.91

4.93

4.93

5.34

5.36

5.37

5.39

6.24

6.25

6.28

6.29

6.61

6.65

7.22

7.23

7.247.

297.

317.

377.

397.

39

OH.

5/16/2012 10:35:54 PM

Acquisition Time (sec) 1.3664 Comment Cinnamyl-allenyl-1 Date 25 Apr 2012 04:16:00Date Stamp 25 Apr 2012 04:16:00File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Cinnamyl-allenyl-1_012001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 2048 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 16384.00SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 10062.3271Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1Cinnamyl-allenyl-1_012001r

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Norm

alize

d Inte

nsity

70.49

76.78

77.10

77.4178

.20

93.89

126.6

412

8.62

130.7

0

136.5

2

207.3

4

OH.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 3:54:14 PM

Acquisition Time (sec) 3.9584 Comment Chloro-allenyl-p Date 18 Apr 2012 23:10:56Date Stamp 18 Apr 2012 23:10:56File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Chloro-allenyl-p_010001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 16 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 128.00SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2455.5339Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.32 (s, 4 H), 5.39 (q, J=6.48 Hz, 1 H), 5.23 (dd, J=4.17, 2.40 Hz, 1 H), 4.86 - 5.00 (m, 2 H), 2.34 (s, 1 H)

VerticalScaleFactor = 1Chloro-allenyl-p_010001r

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alize

d Inte

nsity

1.002.021.034.13

M01(s)

M05(s)

M03(dd)

M02(q) M04(m)

2.344.914.9

24.9

24.9

34.93

4.94

5.22

5.245.3

85.4

05.4

1

7.32

OH

Cl

.

5/16/2012 3:57:46 PM

Acquisition Time (sec) 1.3664 Comment Chloro-allenyl-p Date 19 Apr 2012 05:41:20Date Stamp 19 Apr 2012 05:41:20File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Chloro-allenyl-p_013001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 2048 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 14596.50SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 10062.3271Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1Chloro-allenyl-p_013001r

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Norm

alized

Inten

sity

71.35

77.07

77.3978

.4994.97

127.5

312

8.62

133.4

9141.2

6

207.1

6

OH

Cl

.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 4:26:29 PM

Acquisition Time (sec) 3.9584 Comment P-Br-all-2 Date 06 May 2012 00:00:00Date Stamp 06 May 2012 00:00:00File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\P-Br-all-2_010001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 16 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 90.50SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2400.6772Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.26 - 7.37 (m, 2 H), 7.11 (d, J=8.34 Hz, 2 H), 5.23 (q, J=6.57 Hz, 1 H), 5.01 - 5.09 (m, 1 H), 4.68 - 4.84 (m, 2 H), 2.30 (br. s., 1 H)

VerticalScaleFactor = 1P-Br-all-2_010001r

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alize

d Inte

nsity

1.032.020.992.07

M04(m)

M01(m)

M03(q)

M02(d)

M05(m)

M06(br. s.)

1.13

2.30

4.76

4.76

4.77

4.78

4.79

5.05

5.055.0

75.0

85.2

15.2

35.2

45.2

6

7.10

7.12

7.31

7.31

7.33

7.34

OH

Br

.

5/16/2012 4:29:03 PM

Acquisition Time (sec) 1.3664 Comment P-Br-all-2 Date 06 May 2012 01:16:48Date Stamp 06 May 2012 01:16:48File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\P-Br-all-2_012001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 2048 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 8192.00SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 10035.1045Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1P-Br-all-2_012001r

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Norm

alize

d Inte

nsity

71.13

76.83

77.15

78.20

94.62

121.3

6

127.6

013

1.29

141.5

2

206.9

3

OH

Br

.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 11:00:43 PM

Acquisition Time (sec) 3.9584 Comment Phch2ch2-allenyl2 Date 27 Apr 2012 18:46:24Date Stamp 27 Apr 2012 18:46:24File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Phch2ch2-allenyl2_010001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 16 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 256.00SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2455.4819Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.09 - 7.37 (m, 5 H), 5.28 (q, J=6.57 Hz, 1 H), 4.88 (dd, J=6.69, 2.40 Hz, 2 H), 4.12 - 4.25 (m, 1 H), 2.61 - 2.86 (m, 2 H), 1.82 - 2.00 (m, 2 H), 1.71 (br. s., 1 H)

VerticalScaleFactor = 1Phch2ch2-allenyl2_010001r

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)

0

0.5

1.0

1.5

2.0

2.5

Nor

mal

ized

Inte

nsity

1.232.261.032.041.006.01

M02(q)

M04(m)

M03(dd)

M06(m)

M07(br. s.)M05(m)

M01(m)

1.71

1.86

1.87

1.89

1.91

1.93

2.70

2.71

2.73

2.76

2.78

2.80

4.174.

184.

19

4.21

4.21

4.22

4.874.

884.

894.

895.

265.

275.

295.

31

7.17

7.19

7.20

7.22

7.27

7.29

7.30

OH.

5/16/2012 11:03:52 PM

Acquisition Time (sec) 1.3664 Comment Phch2ch2-allenyl2 Date 28 Apr 2012 04:16:00Date Stamp 28 Apr 2012 04:16:00File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Phch2ch2-allenyl2_012001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 2048 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 8192.00SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 10062.3271Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1Phch2ch2-allenyl2_012001r

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Norm

alize

d In

tens

ity

31.7

4

39.0

2

68.9

376

.7377

.05

77.3

777

.81

94.7

3

125.

8912

8.43

141.

81

207.

07

OH.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

5/16/2012 11:30:04 PM

Acquisition Time (sec) 3.9584 Comment Cy-allenyl-1 Date 04 May 2012 23:57:52Date Stamp 04 May 2012 23:57:52File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Cy-allenyl-1_010001r Frequency (MHz) 400.19Nucleus 1H Number of Transients 16 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zg30 Receiver Gain 143.70SW(cyclical) (Hz) 8278.15 Solvent CHLOROFORM-d Spectrum Offset (Hz) 2405.8555Sweep Width (Hz) 8277.89 Temperature (degree C) 27.000

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 5.09 (q, J=6.57 Hz, 1 H), 4.71 (dd, J=6.57, 2.27 Hz, 2 H), 3.72 - 3.86 (m, 1 H), 1.46 - 1.79 (m, 6 H), 1.23 - 1.40 (m, 1 H), 0.77 - 1.23 (m, 5 H)

VerticalScaleFactor = 1Cy-allenyl-1_010001r

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

7.641.287.860.992.041.00

M02(dd)

M03(m)

M01(q)

M05(m)

M04(m)

M06(m)

0.88

0.89

0.90

1.01

1.05

1.08

1.121.13

1.14

1.29

1.311.52

1.551.

561.61

1.61

1.72

1.721.74

3.78

3.793.

793.

803.

81

3.82

4.704.71

4.72

4.72

5.07

5.08

5.10

5.12

7.13

OH.

5/16/2012 11:34:32 PM

Acquisition Time (sec) 1.3664 Comment Cy-allenyl-1 Date 05 May 2012 00:06:24Date Stamp 05 May 2012 00:06:24File Name C:\Documents and Settings\leletra1\Desktop\Old_Desktop\paper12\NMRs\Cy-allenyl-1_011001r Frequency (MHz) 100.63Nucleus 13C Number of Transients 256 Origin spect Original Points Count 32768Owner nmrsu Points Count 32768 Pulse Sequence zgpg30 Receiver Gain 8192.00SW(cyclical) (Hz) 23980.81 Solvent CHLOROFORM-d Spectrum Offset (Hz) 11045.6777Sweep Width (Hz) 23980.08 Temperature (degree C) 27.000

VerticalScaleFactor = 1Cy-allenyl-1_011001r

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alize

d Inte

nsity

24.43

25.80

25.87

26.27

28.08

28.45

43.9173

.8576

.4977.12

93.04

207.0

4

OH.

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012