NHC Halide Redn Supp Info · Carbohydrate Res. 1992, 230, 327–342. Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry

SUPPORTING INFORMATION

Radical reductions of alkyl halides bearing electron withdrawing

groups with N-heterocyclic carbene boranes

Shau-Hua Ueng,a,b Louis Fensterbank,a Emmanuel Lacôte,a Max Malacria,a and Dennis P. Curran*b

a Institut Parisien de Chimie Moléculaire (UMR CNRS 7201) UPMC Univ Paris 06, 4

place Jussieu, C. 229, 75005 Paris, France.

b University of Pittsburgh, Department of Chemistry,Pittsburgh, PA 15260, USA.

[email protected], [email protected], [email protected],

[email protected]

Table of Contents

General Remarks..................................................................................................... S2

Pilot Reductions of Adamantyl Halides ................................................................... S3

Experimental Procedures, Compound Characterization ........................................... S4

11B NMR Time-course Spectra.............................................................................. S12

Copies of Spectra .................................................................................................. S14

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2011

S2

General Remarks: Chemicals and solvents were purchased from commercial

suppliers and used as received. The benzene used for AIBN-initiated free radical

reactions was deoxygenated by passing a gentle stream of argon through for 20 min

before use. All flash column chromatography was performed with 230–400 mesh

silica gel purchased from Sorbent Technologies as the stationary phase. Proton (1H),

carbon (13C), and boron (11B) nuclear magnetic resonance spectra were measured on a

Bruker Avance 300 instrument at 300 MHz, 75 MHz, and 96.3 MHz, and Bruker

Avance spectrometer fitted with a BBFO probehead at 400, 100, and 128.4 MHz,

respectively. The chemical shifts in spectra were measured in parts per million (ppm)

on the delta (δ) scale relative to the resonance of the solvent peak (CDCl3 signal as

reference, 1H = 7.26 ppm, 13C = 77.0 ppm). 11B chemical shifts are given relative to

BF3•OEt2 (11B = 0 ppm). Unless noted, NMR spectra were recorded in CDCl3 at 300

K. The resonance of the carbene carbon center connected to boron could not be

observed because of the quadrupole broadening. The following abbreviations were

used to describe coupling: s = singlet; d = doublet; t = triplet; q = quartet; br = broad;

m = multiplet. Infrared (IR) spectra were recorded on a Nicolet Avatar 360 FT-IR

spectrometer as thin films (CH2Cl2) on NaCl plates and Bruker Tensor 27 ATR

diamant PIKE spectrometer. Low and high resolution mass spectra were obtained

on a Micromass Inc. Autospec instrument with E-B-E geometry and also recorded by

Structure et fonction de molecules bioactives (UMR 7613) of Université Pierre et

Marie Curie (electrospray source).


S3

Table S1. Pilot reductions of adamantyl halides with 3

XN

NBH3

PhH or tBuPh

H

entry X conditions time solvent [RX] T °C GC yield (%)

1 I Et3B/O2 (1 equiv) 2 h benzene (1 mL) 0.1 M rt 21%

2 I Et3B/O2 (6 equiv) 2 h benzene (1 mL) 0.1 M rt 32% (25% SM)

3 I AIBN (1 equiv) 2 h benzene (1 mL) 0.1 M 80°C 31% (15% SM)

4 I ACCN (1 equiv) 2 h benzene (1 mL) 0.1 M 110°C 64% (14% SM)

5 I ACCN (1 equiv) 2 h toluene (4 mL) 0.025

M 110°C 53% (20% SM) Pressure tube

6 I – 2 h toluene-d8 (0.5 mL) 0.1 M 110°C 9% (80% SM)

7 Br Et3B/O2 (1 equiv) 2 h benzene (1 mL) 0.1M rt 9%

8 Br Et3B/O2 (6 equiv) 2 h benzene (1 mL) 0.1 M rt 12% (82% SM)

9 Br AIBN (1 equiv) 2 h benzene (1 mL) 0.1M 80°C 2% (98% SM)

10 Br ACCN (1 equiv) 2 h toluene (4 mL) 0.025

M 110°C 48% (50% SM) pressure tube

11 Br ACCN (1 equiv) 2 h benzene (1 mL) 0.1 M 80°C 12% (88% SM)

12 Br ACCN (1 equiv) 2 h benzene (1 mL) 0.1 M 80°C 27% (78% SM)

13 Br tBuOOtBu hν 2 h

benzene (0.1 mL)

tert-butylbenzene (0.5 mL)

0.08 M ~60 °C 60% (NMR tube)

14 Br No tBuOOtBu 2 h

benzene (0.1 mL)

tert-butylbenzene (0.5 mL)

0.08 M ~60 °C 0%

ACCN is 1,1'-azobis(cyclohexane-1-carbonitrile)

Dr. Julien Monot also contributed to these results.


S4

OI O

HOO

O H

1,2:5,6-Di-O-isopropylidene-3-iodo-α-D-glucofuranose (5a): Iodine (0.58 g, 2.28

mmol) was added to the solution of diacetone-α-D-glucose (0.5 g, 1.9 mmol),

triphenylphosphine (0.6 g, 2.28 mmol), and imidazole (0.26 g, 3.8 mmol) in of

toluene (12 mL). The brown mixture was reflux for 3 h, and followed by the addition

of sat'd NaHCO3 (aq) (10 mL). The byphase system was partitioned between ethyl ether

(70 mL ) and sat'd NaHCO3 (aq) solution (30 mL). The org. layer was washed with

sat'd Na2S2O3 (aq) (30 mL), water (30 mL) and brine (30 mL), dried (MgSO4), and

concentrated to give a yellow oil. The yellow oil was purified by flash

chromatography (SiO2, elution with hexane : ethyl acetate = 85 : 15) to give the

desired iodide 5a as a white solid (0.38 g, 54 %). 1H NMR (CDCl3, 300 MHz): δ 5.82

(d, J = 3.6 Hz, 1H), 4.61 (t, J = 4.1 Hz, 1H), 4.40–4.23 (m, 2H), 4.20–4.04 (m, 2H),

3.77 (dd, J = 9.9, 4.5 Hz, 1H), 1.56 (s, 3H), 1.50 (s, 3H), 1.38 (s, 6H). Data

correspond to those reported in the literature.1

OBr O

HOO

O H

1,2:5,6-Di-O-isopropylidene-3-bromo-α-D-glucofuranose (5b): Carbon tetra-

bromide (0.76 g, 2.28 mmol) was added to the solution of diacetone-α-D-glucose (0.5

g, 1.9 mmol), triphenylphosphine (0.6 g, 2.28 mmol), and imidazole (0.26 g, 3.8

mmol) in toluene (12 mL). The brown mixture was reflux for 3 h, and followed by the

addition of sat'd NaHCO3 (aq) (10 mL). The byphase system was partitioned between

ethyl ether (70 mL) and 30 mL of sat'd NaHCO3 (aq) solution. The org. layer was 1 Kunz, H.; Schmidt, P. Liebigs Ann. Chem. 1982, 1245–1260.


S5

washed with sat'd Na2S2O3 (aq) (30 mL), water (30 mL) and brine (30 mL), dried

(MgSO4), and concentrated to give a yellow oil. The yellow oil was purified by flash

chromatography (SiO2, elution with hexane : ethyl acetate = 8 : 2) to give the desired

iodide 5b as a white solid (0.17 g, 28 %). 1H NMR (CDCl3, 300 MHz): δ 5.75 (d, J =

3.6 Hz, 1H), 4.62 (t, J = 4.1 Hz, 1H), 4.35–4.23 (m, 1H), 4.15 (dd, J = 9.6, 3.3 Hz),

4.11–3.95 (m, 2H), 3.83 (dd, J = 9.9, 4,5 Hz, 1H), 1.51 (s, 3H), 1.41 (s, 3H), 1.32 (s,

6H). Data correspond to those reported in the literature.2

OO

HOO

O H

1,2:5,6-Di-O-isopropylidene-3-deoxy-α-D-glucofuranose (6): This was prepared

by the conditions listed in Table 1 with 0.1 mmol of starting halides 5a and 5b;

product 6 was isolated (hexane : ethyl acetate = 85 : 15, 10.0−19.3 mg, 41−79 %) as a

colorless liquid. 1H NMR (CDCl3, 300 MHz): δ 5.81 (d, J = 3.7 Hz, 1H), 4.75 (t, J =

4.2 Hz, 1H), 4.23−4.03 (m, 3H), 3.87−3.75 (m, 1H), 2.18 (dd, J = 13.6, 4.2 Hz, 1H),

1.76 (ddd, J = 13.6, 9.6, 4.2 Hz, 1H), 1.50 (s, 3H), 1.42 (s, 3H), 1.35 (s, 3H), 1.31 (s,


OI

AcOAcO

OAcOAc

1,2,3,4-Tetra-O-acetyl-6-iodo-β-D-glucopyranose (9): This was prepared following

the procedure that described the synthesis of 5a with 1,2,3,4-tetra-O-acetyl-

β-D-glucopyranose (0.2 g, 0.57 mmol). The crude product was purified by flash

chromatography (SiO2, elution with hexane : ethyl acetate = 7 : 3) to give iodide 9 as

a white solid (0.187 g, 72 %). 1H NMR (CDCl3, 300 MHz): δ 5.75 (d, J = 8.1 Hz, 1H), 2 Hodosi, G.; Podányi, B.; Kuszmann, J. Carbohydrate Res. 1992, 230, 327–342.


S6

5.26 (t, J = 9.3 Hz, 1H), 5.13 (dd, J = 9.3, 8.1 Hz, 1H), 4.99 (t, J = 9.3 Hz, 1H),

3.65−3.51 (m, 1H), 3.33 (dd, J = 11.1, 3.0 Hz, 1H), 3.16 (dd, J = 11.1, 6.3 Hz, 1H),

2.13 (s, 3H), 2.06 (s, 3H), 2.03 (s, 3H), 2.01 (s, 3H). Data correspond to those

reported in the literature.3

OAcOAcO

OAcOAc

1,2,3,4-Tetra-O-acetyl-6-deoxy-β-D-glucopyranose (10): This was prepared by the

conditions listed in Table 2 with 0.1 mmol of starting halides 9; product 10 was

isolated (hexane : ethyl acetate = 7 : 3, 22.2−23.6 mg, 67−71 %) as a colorless oil. 1H

NMR (CDCl3, 300 MHz): δ 5.68 (d, J = 8.1 Hz, 1H), 5.19 (t, J = 9.5 Hz, 1H), 5.09 (t,

J = 9.0 Hz, 1H), 4.84 (t, J = 9.5 Hz, 1H), 3.78−3.63 (m, 1H), 2.14 (s, 3H), 2.04 (s, 3H),

2.01 (s, 3H), 2.00 (s, 3H), 1.23 (d, J = 6.3 Hz, 3H). Data correspond to those reported

in the literature.4

O O

I

3-Iodo-3,4-dihydrocoumarin (11): 1H NMR (CDCl3, 300 MHz): δ 7.42−7.32 (m,

1H), 7.25−7.15 (m, 2H), 7.15−7.08 (m, 1H), 4.95 (dd, J = 4.5, 3.0 Hz, 1H), 3.49 (dd, J

= 17.4, 4.5 Hz, 1H), 3.11 (dd, J = 17.4, 3 Hz, 1H). Data correspond to those reported

in the literature.5

O O 3,4-Dihydrocoumarin (12): A solution of 3-iodo-3,4-dihydrocoumarin 11 (27.4 mg,

3 Kaszynski, P.; McMurdie, N. D.; Michl, J. J. Org. Chem. 1991, 56, 307–316. 4 Zercher, C. K.; Fedor, L. R. Carbohydrate Res. 1987, 165, 299–305. 5 Murakata, M.; Jono, T.; Shoji, T.; Moriy, A.; Shirai, Y. Tetrahedron: Asymm. 2008, 19, 2479–2483.


S7

0.1 mmol) and dimethylimidazolylidene borane 3 (11.0 mg, 0.1 mmol) in of

benzene-d6 (1 mL ) was placed in a NMR tube, and the reaction progress was

monitored by 1H NMR spectroscopy until the conversion of the starting material was

complete. 1,3,5-Trimethoxybenzene (11.8 mg, 0.07 mmol) was added to the reaction

solution as the internal standard, and the yield was determined by 1H NMR

spectroscopy analysis (70 %). The resulting product was purified by flash

chromatography (SiO2, pentane : ethyl ether = 8 : 2) to give 12 as a colorless oil (8.9

mg, 60 %). 1H NMR (CDCl3, 300 MHz): δ 7.32−7.15 (m, 2H), 7.11 (d, J = 7.5 Hz,

1H), 7.05 (d, J = 8.7 Hz, 1H), 3.01 (dd, J = 7.5, 6.9 Hz, 2H), 2.79 (dd, J = 6.9, 5.4 Hz,

2H), Data correspond to those reported in the literature.6

TsN

I

TsN

Cl

TsHN

I II 15a

KOHBu4NBr

1-Bromo-2-chloroethane

THF, rt

73 %

NaI

DMF, 80 oC

55 %

N-Allyl-N-(2-chloro-ethyl)-4-methyl-benzenesulfonamide (II): Tetrabutyl-

ammonium bromide (0.6 mmol) was added to a solution of I (6.0 mmol), potassium

hydroxide (9.0 mmol), and 1-bromo-2-chloroethane (9.0 mmol) in THF (30 mL). The

white mixture was stirred at room temperature for 16 h, and then partitioned between

ethyl ether (100 mL) and water (40 mL). The organic layer was washed with water

(40 mL), brine (40 mL), dried (MgSO4), and concentrated. The crude product was

purified by flash chromatography (SiO2, ethyl acetate : pentane = 1 : 9 then 2 : 8) to

afford the chloride II as a colorless oil (1.2 g, 73 %). IR (neat, cm-1) νmax 2930, 1710,

1598, 1451, 1340, 1156, 1091; 1H NMR (CDCl3, 400 MHz) δ 7.71 (d, J = 8.3 Hz, 2H),

7.32 (d, J = 8.3 Hz, 2H), 5.75−5.57 (m, 1H), 5.25−5.12 (m, 2H), 3.83 (d, J = 7.5 Hz,

6 Hwu, J. R.; Wein, Y. S.; Leu, Y.-J. J. Org. Chem. 1996, 61, 1493–1499.


S8

2H), 3.62 (t, J = 7.4 Hz, 2H), 3.37 (t, J = 7.4 Hz, 2H), 2.44 (s, 3H); 13C NMR (CDCl3,

100 MHz) δ 144.4, 137.0, 133.5, 130.5, 127.9, 120.3, 52.8, 49.5, 42.4, 22.2; HRMS

calcd. for C12H16O2NClNaS ([M+Na]+) 296.0482, found 296.0483.

N-Allyl-N-(2-iodo-ethyl)-4-methyl-benzenesulfonamide (15a): Sodium iodide (15

mmol) was added to a solution of chloride II (3.0 mmol) in DMF (7 mL). The

colorless solution was stirred at 80 oC for 16 h, and then cooled to room temperature.

The white resulting mixture was partitioned between ethyl ether (100 mL) and water

(40 mL). The organic layer was washed with water (40 mL), brine (40 mL), dried

(MgSO4), and concentrated. The crude product was purified by flash chromatography

(SiO2, ethyl acetate : pentane = 1 : 9) to afford the iodide 15a as a colorless oil (0.6 g,

55 %). 1H NMR (CDCl3, 400 MHz) δ 7.76−7.65 (m, 2H), 7.32 (d, J = 8.5 Hz, 2H),

5.76−5.60 (m, 1H), 5.27−5.12 (m, 2H), 3.85−3.73 (m, 2H), 3.50−3.35 (m, 2H),

3.30−3.15 (m, 2H), 2.44 (s, 3H). Data correspond to those reported in the literature.7

N-Allyl-N-(2-bromo-ethyl)-4-methyl-benzenesulfonamide (15b): Bromide 15b was

prepared following established procedures.8,9 1H NMR (CDCl3, 400 MHz) δ 7.70 (d, J

= 8.0 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 5.76−5.60 (m, 1H), 5.26−5.13 (m, 2H), 3.81

(d, J = 6.6 Hz, 2H), 3.50−3.35 (m, 4H), 2.43 (s, 3H). Data correspond to those


TsN

3-Methyl-1-(toluene-4-sulfonyl)-pyrrolidine (16): This was prepared by the

7 Ohmiya, H.; Wakabayashi, K.; Yorimitsu, H.; Oshima, K. Tetrahedron 2006, 62, 2207−2213. 8 Miyata, O.; Ozawa, Y.; Ninomiya, I.; Naito, T. Tetrahedron 2000, 56, 6199−6208. 9 Rai, K. M. L.; Hassner, A. Heterocycles 1990, 30, 817.


S9

conditions listed in Table 2 with 0.1 mmol of corresponding substrate; product 16 was

isolated (pentane : ethyl acetate = 9 : 1 then 8 : 2) as a colorless liquid. 1H NMR

(CDCl3, 400 MHz) δ 7.70 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 3.42 (dd, J =

9.6, 7.2 Hz, 1H), 3.38−3.30 (m, 1H), 3.28−3.15 (m, 1H), 2.74 (dd, J = 9.6, 7.9 Hz,

1H), 2.43 (s, 3H), 2.16−2.05 (m, 1H), 1.95−1.80 (m, 1H), 1.42−1.28 (m, 1H), 0.91 (d,

J = 6.6 Hz, 3H). Data correspond to those reported in the literature.10

TsN

Br

O

N-Allyl-N-(2-bromo-acetyl)-4-methyl-benzenesulfonamide (17): NaH (60 % in

mineral oil) (92 mg, 2.31 mmol) was added to the solution of I (0.325 g, 1.54 mmol)

in THF (10 mL) at room temperature in one portion, before the addition of

bromoacetyl bromide (0.37 g, 1.85 mmol). The yellow mixture was stirred at room

temperature for 18 h, and then the yellow reaction mixture was partitioned between of

ethyl ether (70 mL) and water (30 mL). The org. layer was washed with water (30

mL), brine (30 mL), dried (MgSO4), and concentrated to give a yellow oil. The yellow

oil was purified by flash chromatography (SiO2, ethyl acetate : pentane = 1 : 9) to give

the desired product 17 as a colorless oil (0.25 g, 49 %). 1H NMR (CDCl3, 300 MHz) δ

7.83 (d, J = 8.1 Hz, 2H), 7.36 (d, J = 8.1 Hz, 2H), 5.95−5.75 (m, 1H), 5.33−5.18 (m,

2H), 4.46 (d, J = 6.6 Hz, 2H), 4.23 (s, 2H), 2.46 (s, 3H). Data correspond to those


10 Tang, J.; Shinokubo, H.; Oshima, K. Tetrahedron 1999, 55, 1893−1904. 11 Ozaki, S.; Matsushita, H.; Ohmori, H. J. Chem. Soc., Perkin Trans. 1 1993, 2339–2344.


S10

TsNO

4-Methyl-1-(toluene-4-sulfonyl)-pyrrolidin-2-one (18): This was prepared by the

conditions listed in Table 2 with 0.1 mmol of 17; product 18 was isolated (hexane :

ethyl acetate = 9 : 1 then 7 : 3, 2.8−10.6 mg, 11−42 %) as a colorless oil. 1H NMR

(CDCl3, 300 MHz) δ 7.91 (d, J = 8.1 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H), 4.03 (dd, J =

9.9, 7.2 Hz, 1H), 3.41 (dd, J = 9.9, 6.3 Hz, 1H), 2.57 (dd, J = 16.6, 8.1 Hz, 1H),

2.52−2.38 (m overlapped with s at 2.44, 4H), 2.06 (dd, J = 16.6, 7.2 Hz, 1H), 1.09 (d,

J = 6.6 Hz, 3H). Data correspond to those reported in the literature.11

TsNO

N-Acetyl-N-allyl-4-methyl-benzenesulfonamide (19): This was prepared by the

conditions listed in Table 2 with 0.1 mmol of 17; product 19 was isolated (hexane :

ethyl acetate = 9 : 1 then 7 : 3, 6.8−14.7 mg, 27−58 %) as a colorless oil. 1H NMR

(CDCl3, 300 MHz) δ 7.81 (d, J = 8.1 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H), 5.98−5.80 (m,

1H), 5.33−5.20 (m, 2H), 4.46 (dt, J = 5.7, 1.5 Hz, 2H), 2.44 (s, 3H), 2.29 (s, 3H). Data

correspond to those reported in the literature.11

TsNO

Br

N-Allyl-N-(2-bromo-propionyl)-4-methyl-benzenesulfonamide (20): This was

prepared following the procedure described the synthesis of 17 with I (1.54 mmol)

and of 2-bromopropionyl bromide (1.85 mmol). The crude product was purified by

flash chromatography (SiO2, ethyl acetate : pentane = 15 : 85) to give the desired

product 20 as a white solid (0.38 g, 71 %). 1H NMR (CDCl3, 300 MHz) δ 7.87 (d, J =


S11

8.1 Hz, 2H), 7.35 (d, J = 8.1 Hz, 2H), 6.00−5.83 (m, 1H), 5.33−5.20 (m, 2H), 4.86 (q,

J = 6.6 Hz, 1H), 4.70 (dd, J = 17.4, 4.2 Hz, 1H), 4.41 (dd, J = 17.4, 5.4 Hz, 1H), 2.45

(s, 3H), 1.74 (d, J = 6.6 Hz, 3H). Data correspond to those reported in the literature.12

TsNO

trans-3,4-Dimethyl-1-(toluene-4-sulfonyl)-pyrrolidin-2-one (trans-21): This was

prepared by the conditions listed in Table 2 with 0.1 mmol of 20; product 21 was

isolated (hexane : ethyl acetate = 9 : 1 then 7 : 3, 6.8−14.7 mg, 36−44 %) as a

colorless oil. 1H NMR (DMSO-d6, 300 MHz) δ 7.83 (d, J = 8.1 Hz, 2H), 7.44 (d, J =

8.1 Hz, 2H), 3.98 (dd, J = 9.3, 7.5 Hz, 1H), 3.28 (t, J = 9.6 Hz, 1H), 2.40 (s, 3H),

2.22−2.10 (m, 1H), 2.03−1.85 (m, 1H), 1.03 (d, J = 6.3 Hz, 3H), 0.96 (d, J = 6.9 Hz,


TsNO

N-Allyl-4-methyl-N-propionyl-benzenesulfonamide (22): Following corresponding

conditions with 0.1 mmol of 20, a mixture of compounds 22, I, and rest of the AIBN

was isolated (hexane : ethyl acetate = 9 : 1 then 7 : 3) as a colorless oil. The percent

yield of amide 22 was determined by 1H NMR spectroscopy analysis as 17–28 %. 1H

NMR (CDCl3, 300 MHz) δ 7.82 (d, J = 8.1 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H),

5.98–5.82 (m, 1H), 5.33–5.20 (m, 2H), 4.48 (d, J = 8.4 Hz, 2H), 2.56 (q, J = 7.3 Hz,

2H), 2.45 (s, 3H), 1.04 (t, J = 7.3 Hz, 3H). Data correspond to those reported in the

literature.12

12 Ozaki, S.; Matsushita, H.; Emoto, M.; Ohmori, H. Chem. Pharm. Bull. 1995, 43, 32–36.


S12

0 -20 -40 -60 ppm

(a)

(b)

N

NBH3

I2 (0.5 equiv)

N

NBH2I

unidentifiedspecies

NaBH484 %

3 23a

Figure S1. Partial 11B NMR spectra [96.3 MHz, Benzene-d6, 298 K] displaying (a-b)

the formation of the 1,3-dimethylimidazol-2-ylidene borane 3 from monoiodide

intermediate 23a under the treatment with NaBH4 over time—(a) 0 min, (b) 30 min,

after addition of 2 equiv of NaBH4.


S13

0 -20 -40 -60 ppm

(a)

(b)

(c)

(d)

N

NBH2

h!, 15 mind-Benzene, 60 oC

OBr

O

N

NBH2Br

NaBH4

77 %

3 23b

Figure S2. Partial 11B NMR spectra [96.3 MHz, Benzene-d6, 298 K] displaying (a-d)

the formation of the 1,3-dimethylimidazol-2-ylidene borane 3 from monobromide

intermediate 23b under the treatment with NaBH4 over time and the loading scale of

NaBH4—(a) 0 min, after irradiation for 15 min (b) 10 min, 0.5 equiv of NaBH4 (c) 20

min, 1.5 equiv of NaBH4, and (d) 180 min, 2 equiv of NaBH4.


OI O

HOO

O H

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 0.5 ppm

1.378

1.498

1.560

1.567

3.748

3.763

3.781

3.796

4.042

4.065

4.070

4.093

4.115

4.136

4.144

4.164

4.242

4.255

4.276

4.288

4.304

4.317

4.326

4.339

4.347

4.593

4.607

4.620

5.818

5.830

7.260

6.88

3.64

5.55

1.07

2.32

0.60

0.74

0.88

1.05

1.00

shu2099b, 08−19−09, 301bSupplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2011

OBr O

HOO

O H

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 0.5 ppm

1.316

1.414

1.513

3.810

3.825

3.843

3.858

3.975

3.999

4.003

4.027

4.034

4.055

4.063

4.084

4.130

4.142

4.163

4.174

4.269

4.280

4.291

4.303

4.313

4.325

4.604

4.617

4.631

5.745

5.757

7.260

6.98

3.41

3.27

1.14

2.40

1.10

1.10

1.06

1.00

shu2100a, 08−20−09, 301bSupplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2011

OO

HOO

O H

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 0.5 ppm

1.362

1.397

1.416

1.430

1.450

1.484

1.502

1.518

1.711

1.727

1.744

1.756

1.760

1.772

1.789

1.805

2.146

2.160

2.192

2.205

3.777

3.798

3.806

3.816

3.823

3.831

3.845

4.065

4.071

4.086

4.103

4.112

4.114

4.126

4.130

4.144

4.151

4.156

4.170

4.189

4.731

4.745

4.760

5.783

5.800

5.813

7.259

4.23

2.97

3.37

3.35

1.21

1.06

1.10

3.31

1.04

1.00


OI

AcOAcO

OAcOAc

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 0.5 ppm

1.577

2.014

2.033

2.063

2.131

3.129

3.151

3.167

3.188

3.302

3.312

3.339

3.349

3.534

3.544

3.555

3.566

3.576

3.587

3.597

4.957

4.988

5.019

5.102

5.130

5.134

5.161

5.224

5.255

5.286

5.734

5.761

7.261

3.21

3.00

3.14

3.09

1.08

1.08

1.08

0.98

0.97

1.02

1.00

shu3035a, 11−06−09, 301aSupplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2011

OAcOAcO

OAcOAc

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 0.5 ppm

1.219

1.240

1.267

1.627

1.719

1.874

1.977

1.995

2.013

2.035

2.083

2.094

2.140

3.654

3.674

3.695

3.707

3.727

4.810

4.842

4.873

5.059

5.091

5.119

5.163

5.194

5.226

5.665

5.692

7.243

7.258

7.268

7.394

3.56

2.93

2.96

2.96

2.61

1.01

0.98

1.04

1.08

1.00


O O

I

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 0.5 ppm

1.547

3.072

3.082

3.130

3.140

3.449

3.452

3.464

3.467

3.507

3.522

3.525

4.938

4.947

4.952

4.962

7.103

7.129

7.153

7.157

7.178

7.182

7.195

7.197

7.200

7.203

7.220

7.230

7.248

7.258

7.307

7.325

7.328

7.335

7.346

7.352

1.11

1.12

1.00

1.09

2.21

1.06

shu3045b, 11−11−09, 301bSupplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2011

O O

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 0.5 ppm

1.252

1.431

1.574

2.772

2.794

2.800

2.820

2.989

3.014

3.037

7.043

7.071

7.100

7.125

7.189

7.212

7.233

7.261

7.284

2.00

2.10

1.59

1.96


1.94

89

1.97

03

1.00

00

2.02

23

2.00

83

2.01

46

2.02

58

2.97

39

Inte

gral

7.71

977.

7148

7.70

337.

6989

7.33

017.

3285

7.30

887.

2600

5.71

935.

7034

5.69

525.

6869

5.67

875.

6765

5.66

235.

6601

5.65

135.

6453

5.64

375.

6354

5.61

905.

2229

5.21

965.

2163

5.21

305.

2059

5.20

315.

1999

5.19

715.

1790

5.17

575.

1725

3.83

883.

8361

3.83

343.

8230

3.81

973.

8169

3.63

673.

6186

3.61

583.

5994

3.39

183.

3726

3.35

452.

4351

1.55

90

(ppm)0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0

shu2112a

TsN

Cl


shu2112a

144.

3512

137.

0253

133.

5209

130.

5134

127.

8830

120.

3429

77.9

984

77.6

814

77.3

643

52.8

076

49.4

746

42.4

229

22.1

931

(ppm)020406080100120140160180200220240260

TsN

Cl


1.90

11

2.05

42

1.00

00

2.00

97

1.83

80

1.85

641.

8332

2.88

48

Inte

gral

7.72

137.

7120

7.70

767.

7005

7.69

567.

6912

7.33

127.

3296

7.30

997.

2605

5.71

605.

6996

5.69

135.

6886

5.67

495.

6727

5.66

395.

6480

5.63

165.

2985

5.21

635.

2130

5.20

925.

2042

5.20

105.

1982

5.19

495.

1763

5.17

305.

1703

3.80

383.

7901

3.78

733.

4449

3.42

683.

4202

3.40

443.

2559

3.23

893.

2350

3.23

293.

2153

3.21

372.

4367

1.55

19

(ppm)0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0

shu2117c

TsN

I


2.00

00

2.02

39

1.00

54

2.04

64

2.00

55

4.18

70

3.09

18

Inte

gral

7.71

377.

6928

7.32

967.

3099

7.25

89

5.71

875.

7023

5.69

415.

6864

5.67

765.

6765

5.65

965.

6508

5.64

315.

6349

5.61

85

5.21

855.

2157

5.20

265.

2010

5.17

52

3.81

753.

8010

3.47

613.

4657

3.45

153.

4471

3.43

503.

4246

3.41

153.

3939

3.38

302.

4340

(ppm)0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0

shubromide

TsN

Br


2.00

00

1.98

46

1.01

771.

0389

1.04

35

0.97

24

2.99

62

1.00

67

1.05

82

1.13

21

2.94

85

Inte

gral

7.71

647.

6956

7.32

197.

3203

7.30

167.

3005

7.26

00

3.43

723.

4191

3.41

313.

3950

3.36

443.

3539

3.34

353.

3397

3.33

313.

3293

3.31

943.

3085

3.24

273.

2241

3.22

193.

2181

3.20

383.

1994

3.19

723.

1792

2.76

332.

7436

2.73

922.

7195

2.42

582.

1381

2.11

842.

1009

2.08

171.

9343

1.92

391.

9168

1.90

531.

9003

1.89

271.

8866

1.87

571.

8691

1.85

811.

3924

1.37

161.

3612

1.35

081.

3409

1.33

001.

3196

1.29

871.

2505

0.91

740.

9108

0.90

09

(ppm)0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0

shu2122c

1.01

77

1.03

89

1.04

35

0.97

24

Inte

gral

3.41

913.

4131

3.39

503.

3644

3.35

393.

3435

3.33

973.

3331

3.32

933.

3194

3.30

853.

2427

3.22

413.

2219

3.21

813.

2038

3.19

943.

1972

3.17

922.

7633

2.74

362.

7392

2.71

95

(ppm)2.83.03.23.43.63.8

TsN


TsN

Br

O

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 0.5 ppm

1.560

2.044

2.455

4.225

4.449

4.453

4.457

4.468

4.471

5.220

5.222

5.227

5.232

5.253

5.256

5.289

5.293

5.298

5.785

5.803

5.820

5.837

5.856

5.860

5.877

5.894

5.913

7.259

7.317

7.343

7.370

7.821

7.848

7.893

7.921

3.72

2.31

2.50

2.43

1.00

2.22

2.00


TsNO

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 0.5 ppm

1.079

1.101

1.248

1.390

1.600

2.022

2.046

2.077

2.101

2.435

2.472

2.495

2.516

2.525

2.551

2.580

2.607

3.383

3.404

3.416

3.437

3.629

3.997

4.021

4.030

4.054

7.260

7.319

7.346

7.900

7.923

7.928

2.97

1.06

4.07

1.62

1.03

1.00

2.35

2.16

shu3104b, 12−09−09, 301Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2011

TsNO

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 0.5 ppm2.290

2.440

4.445

4.450

4.454

4.463

4.468

4.473

5.219

5.223

5.249

5.252

5.257

5.301

5.306

5.309

5.816

5.834

5.850

5.852

5.868

5.873

5.887

5.891

5.907

5.910

5.925

5.944

7.259

7.316

7.318

7.345

7.784

7.790

7.796

3.09

3.24

2.06

2.06

1.00

2.11

2.00


TsNO

Br

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 0.5 ppm

1.550

1.732

1.754

2.450

4.094

4.118

4.286

4.307

4.371

4.389

4.429

4.447

4.664

4.670

4.673

4.679

4.721

4.728

4.737

4.742

4.822

4.844

4.866

4.888

5.200

5.236

5.273

5.291

5.301

5.855

5.872

5.889

5.907

5.912

5.924

5.929

5.947

5.964

5.981

7.261

7.333

7.360

7.785

3.62

3.93

0.21

1.24

1.24

1.09

2.53

1.00

2.46

0.09

1.85

0.33

shu3044c, 11−12−09, 301aSupplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2011

TsNO

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 0.5 ppm

0.945

0.968

1.021

1.042

1.904

1.916

1.927

1.938

1.948

1.960

1.962

1.971

1.995

2.102

2.125

2.139

2.148

2.162

2.171

2.185

2.379

2.401

2.493

2.498

2.504

3.250

3.282

3.302

3.314

3.345

3.393

3.951

3.976

3.982

4.007

7.426

7.453

7.817

7.845

3.05

3.09

1.03

1.02

3.38

1.27

1.03

2.19

2.00

shu3071b_2, 11−24−09, 301aSupplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2011

TsNO

+ TsHN

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 0.5 ppm

1.018

1.042

1.066

1.093

1.117

1.141

1.248

1.500

1.542

1.568

1.666

1.674

1.722

1.741

1.756

1.774

1.940

2.411

2.435

2.447

2.528

2.552

2.576

2.601

4.281

4.302

4.463

4.468

4.473

4.481

4.486

4.491

5.193

5.197

5.223

5.227

5.240

5.245

5.249

5.257

5.261

5.297

5.302

5.306

5.845

5.879

7.258

7.312

7.339

7.803

7.831

7.890

7.896

7.912

7.918

3.18

35.5

1

6.49

1.93

1.05

1.96

3.06

1.43

4.23

2.00

2.06

shu3071a, 11−21−09, 301Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2011

Documents

NHC Halide Redn Supp Info · Carbohydrate Res. 1992, 230, 327–342. Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry