[摘要]:A stereocontrolled asymmetric synthesis of the C7-C16 fragment of bryostatins is described. The key steps involved were a Jacobsen's hydrolytic kinetic resolution and a Reformatsky reaction to build the C11-C16 fragment. A vinyl Grignard reagent was used to construct the C7-C10 fragment. The C11-C16 and C7-C10 fragments were coupled by means of a cross-metathesis reaction to give a key intermediate. The pyran ring system was constructed by means of an oxa-Michael reaction. |