Upload
truongngoc
View
254
Download
1
Embed Size (px)
Citation preview
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
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
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.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
(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.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
(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.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
(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.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
(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.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
(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.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
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.
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 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