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

Experimental for chapter 3.1
5.3 Experimental Procedures for Chapter 3.1
Synthesis of (S,S)-hydrobenzoin (176)
OH
Ph AD mix α, Me 2 SO 2 NH 2
HO
Ph
Ph
t-BuOH/H 2 O
Ph
By the Method of Sharpless 8 AD mix-α (45.93 g) and methylsulfonamide (4.70 g, 42.3
mmol) were dissolved in t-BuOH (255 cm 3 ) and water (255 cm 3 ) with vigorous stirring
and cooled to 0 °C. trans-Stilbene (6.00 g, 33.3 mmol) was added to the solution and
stirred for 48 hr. Sodium sulfite (50 g) was added with stirring and allowed to warm to
ambient temperature before being partitioned in a separating funnel. The organic
phase was concentrated under vacuum and recombined with the aqueous phase,
washed with CH 2 Cl 2 (3 x 150 cm 3 ), brine (3 x 200 cm 3 ), and the combined organic
phases dried over Na 2 SO 4 , and solvent concentrated under vacuum. The residue was
purified by flash chromatography (2:1 EtOAc:petrol) to give hydrobenzoin 176 (7.01
g, 98%) as colourless needles.
R f : 0.36 (1:2 petrol:EtOAc); Mpt: 146-147 ºC (petrol/EtOAc), lit. 9 148-150 ºC; [α] 23 D :
–94 (c = 1.0, EtOH), lit. 9 –94.1 (c = 1, EtOH); MS m/z (CI + ): 232 (MNH + 4 , 100%),
215 (MH + , 32%); IR ν max /cm -1 : 3498 (br, O–H), 2921, 2896, 1451, 1199, 1045;
Microanalysis: % found (% calc’d for C 14 H 14 O 2 ) C, 78.73 (78.48); H, 6.73 (6.59); 1 H-
NMR (DMSO, 300 MHz) δ 7.21-7.15 (m, 6H, Ph); 7.11-7.08 (m, 4H, Ph); 5.38* (s,
2H, OH); 4.59 (s, 2H, CH); 13 C-NMR (DMSO, 75 MHz) δ 143.1 (ipso-Ph); 128.0,
127.9, 127.4 (Ph); 78.4 (CH).
Synthesis of (4S,5S)-4,5-diphenyl-1,3-dioxolan-2-one (177)
O
OH
HO
CDI
O O
Ph
Ph
Ph Ph
To a stirred solution of (S,S)-hydrobenzoin (3.27 g, 15.2 mmol) in CH 2 Cl 2 (25 cm 3 )
was added CDI (3.71 g, 22.9 mmol). Aqueous hydrochloric acid (50 cm 3 , 1N) was
added after 6 hr and the mixture washed with CH 2 Cl 2 (2 x 50 cm 3 ), EtOAc (50 cm 3 ),
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