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

Experimental for chapter 4.1
combined organic layers washed with brine before being dried over sodium sulphate.
Removal of solvent gave a white crystalline solid which was purified by
recrystallisation from diethyl ether to give colourless cubes of allyl alcohol 213 (216
mg, 98%)
R f : 0.31 (1:1, petrol:EtOAc); Mpt: 155-156 ºC (Et 2 O); [α] 25 D : +174 (c = 1.0, CHCl 3 );
MS m/z (CI+) 392 (100%, MH + ), 393 (24%, (M+1)H + ), 303 (15%, [M-PhCH] + ), 285
(22%, [M-PhCHO] + ); HRMS: found 392.2228, MH requires 392.2220; Microanalysis
found (%): C 75.03, H 7.56, N 3.48, C 25 H 29 NO 3 requires (%): C 76.70, H 7.47, N 3.58;
IR ν max (film)/cm⎯¹ 3359 (br, OH), 2970 (m, C-H), 1638 (C=N), 1050 (C-OH); ¹H-
NMR (CDCl 3 , 500 MHz) δ 7.33-7.25 (m, 5H, Ph), 7.24-7.20 (m, 1H, Ph), 7.20-7.16
(m, 2H, Ph), 7.15-7.11 (m, 2H, Ph), 5.53 (d, 1H, J 10.0, H6), 5.44 (d, 1H, J 10.0, H5),
5.07 (d, 1H, J 10.5, CHOPh), 4.94 (d, 1H, J 10.5, CHNPh), 3.93-3.87 (m, 2H, H4, H3),
3.32 (br s, 1H, OH), 2.44 (br s, 1H, OH), 2.23 (p, 1H, J 7.0, CHMe 2 ), 1.51 (d, 1H, J
10.5, H2), 1.37 (s, 3H, Me), 1.09 (d, 3H, J 7.0, CHMe a Me b ), 1.00 (d, 3H, J 7.0,
CHMe a Me b ); ¹H-NMR (C 6 D 6 , 300 MHz) δ 7.28-7.22 (m, 2H, Ph), 7.20-7.03 (m, 8H,
Ph), 5.64 (d, 1H, J 10.0, H6), 5.45 (dd, 1H, J 10.0, 2.0, H5), 5.12 (s, 2H, CHPh), 4.21
(ddd, 1H, J 11.5, 7.5, 2.0, H3), 4.04 (br d, 1H, J 7.5, H4), 2.89 (br s, 2H, OH), 2.41 (p,
1H, J 7.0, CHMe 2 ), 1.64 (d, 1H, J 11.5, H2), 1.40 (s, 3H, Me), 1.36 (d, 3H, J 7.0,
CHMe a Me b ), 1.33 (d, 3H, J 7.0, CHMe a Me b ); ¹³C-NMR (CD 3 OD, 75.5 MHz) δ 171.8
(C=N), 140.8 (ipso-Ph), 138.4 (ipso-Ph), 132.5 (C5), 129.2 (C6), 128.7, 127.9, 127.0,
126.3 (Ph), 90.6 (CHOPh), 77.5 (CHNPh), 74.7 (CHOH), 72.7 (CHOH), 53.1 (C2),
44.3 (C1), 26.9 (CHMe 2 ), 25.7 (CHMe a Me b ), 25.5 (Me), 17.0 (CHMe a Me b ).
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