Chlorotrimethylsilane → HCID 71270603, compound

Participants

Reaction Conditions

Reaction Steps

To a solution of dipropylamine (212 mL, 1.55 mol) in 2-methoxy-2-methylpropane (2000 mL) at −15° C. under a blanket of nitrogen, 2.50 M of n-butyllithium in hexane (567 mL, 1.42 mol) was added slowly over 10 minutes, maintaining a temperature of less than −10° C. The resulting white suspension was stirred for 30 minutes at −15° C. To this suspension was added (1S,2R,3S,5R)-3-(benzyloxy)-2-(benzyloxymethyl)-6-oxabicyclo[3.1.0]hexane (21) (400.00 g, 1.29 mol) slowly as a solution in methyl tert-butyl ether (1200 mL) over 30 minutes, maintaining an internal temperature of less than −10° C. The reaction mixture was stirred for 30 minutes at −15° C. TLC analysis indicated no remaining starting material (20% ethyl acetate/heptane). Chlorotrimethylsilane (204 mL, 1.61 mol) was added while maintaining a temperature of less than −10° C. The mixture was allowed to warm to 0° C. and stirred for 30 minutes. TLC analysis indicated that no alcohol intermediate (20% ethyl acetate/heptane). The reaction mixture was quenched with the slow addition of water (4 L) while maintaining an internal temperature of less than 8° C. The aqueous layer was separated and the organic layer was extracted 3 times with water (3×4 L) and once with saturated sodium chloride in water (4 L). The organic layer was concentrated under reduced pressure to give an orange oil (480 g, 97.4%) which was used without further purification. 1H NMR (300 MHz, CD3OD, δ): 7.18 (m, 10H), 5.65 (s, 1H), 4.55 (t, 1H), 4.30 (m, 5H), 4.02 (s, 2H), 2.58 (m, 1H), 1.47 (m, 1H) and 0.00 (s, 9H).

Provenance & Evidence