A Route to Carbasugar Analogues - Jonathan Clayden - The ...

Experimental for chapter 3.1
Synthesis of N-((1R,2S)-2-hydroxy-1,2-diphenylethyl)-4-methoxybenzamide
(165b)
Ph
O Cl
Ph HO
Ph
Ph
NH 2
O NH
1
OH
2
Et 3 N
3
OMe
4
OMe
General procedure 1 was used mixing para-anisoyl chloride (13.9 g, 81.5 mmol) with
(1R,2S)-(−)-2-amino-1,2-diphenylethanol 174 (20.0 g, 93.8 mmol) and triethylamine
(22.5 cm 3 , 163 mmol) to give the title amide (25.3 g, 98%) as a colourless powder.
R f : 0.42 (2:1 petrol:EtOAc); Mpt: 240-244 °C (EtOAc); [α] 25 D : +41 (c = 0.4, DMSO);
MS m/z (CI+): 348 (100%, MH + ), 349 (27%, (M+1)H + ), 330 (57%, [M-H 2 O] + ), 96
(61%); HRMS (ESI+) m/z found 348.1586 (MH calcd. 348.1594); IR ν max (film)/cm -1 :
3334 (s, OH), 1632 (C=O), 1526; 1 H-NMR (MeOD, 300 MHz) δ 7.58 (d, 2H, J 9.0,
ortho-Ph), 7.44-7.17 (m, 10H, Ph), 6.92 (d, 2H, J 9.0, meta-Ph), 5.32 (d, 1H, J 8.0,
CHOH), 5.05 (d, 1H, J 8.0, CHN), 3.81 (s, 3H, OMe); 13 C-NMR (DMSO, 125 MHz) δ
164.9 (CO), 161.8 (ipso-Ph), 144.1 (ipso-Ph), 142.0, 129.3, 128.7, 128.0, 127.9, 127.3,
127.2, 127.1, 127.0 (Ar), 113.7 (C3), 74.9 (COH), 59.3 (CNH), 55.7 (OMe).
Synthesis of N-((1R,2S)-2-hydroxy-1,2-diphenylethyl)-3-methoxybenzamide
(165c)
Ph
O Cl
Ph
Ph
NH 2
OH
OMe Et 3 N
Ph
HO
O NH
6
5
4
1
2
3
OMe
General procedure 1 was used mixing meta-anisoyl chloride (0.30 cm 3 , 2.12 mmol)
with the amino alcohol 174 (500 mg, 2.34 mmol) and triethylamine (0.6 cm 3 , 4.25
mmol) to give amide 165c (710 mg, 96%) as colourless needles.
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