ASSEMBLY OF THE SOUTHERN MACROCYCLIC HALF OF (+)-SPIRASTRELLOLIDE A THROUGH CYCLIC ACETAL TETHERED RING-CLOSING METATHESIS AND 1,3-ANTI-MUKAIYAMA-ALDOL

作者：Tang Yu^*; Yang Jin Haek; Liu Jia; Wang Chao Chao; Lv Ming Can; Wu Yi Biao; Yu Xue Liang; Ko Changhong; Hsung Richard P

来源：Heterocycles, 2012, 86(1): 565-598.

DOI：10.3987/COM-12-S(N)54

• Spirastrellolide A
• Natural Product Synthesis
• Cyclic Acetal Tethered RCM
• Spiroketal Synthesis
• Mukaiyama Aldol

We describe herein details of our efforts in syntheses of A-ring and BC-ring of (+)-spirastrellolide A. While the former would constitute a facile 12-step synthetic endeavor starting from 1,5-pentanediol, the latter would showcase a cyclic acetal-tethered ring-closing metathesis [RCM] method that was developed in our lab for de novo synthesis of spiroketals. Constructing the entire Southern Half of the macrocycle would require 1,3-anti-Mukaiyama aldol addition for connecting A-ring and BC-ring specifically at C10 and C11, thereby culminating a 17-step approach for the Southern Macrocyclic Half linearly from (+)-2,3-(O)-iso-propylidene-L-threitol. Also discussed here is the possibility of pursuing a more convergent approach toward the assembly of the Southern Half through first connecting A-ring and C-ring via acetal formation that would first link together the free C13-OH with C17 at the spiro-BC-ring junction. An ensuing application of our cyclic acetal-tethered RCM strategy to close B-ring would adopt this cyclic acetal intermediate.

• 出版日期2012-12-31
• 单位天津大学