(+)-Vincadifformine、(-)-Quebrachamine、(+)-Aspidospermidine、(-)-Aspidospermine、(-)-Pyrifolidine 及相关天然产物的发散不对称全合成
Divergent Asymmetric Total Synthesis of (+)-Vincadifformine, (-)-Quebrachamine, (+)-Aspidospermidine, (-)-Aspidospermine, (-)-Pyrifolidine, and Related Natural Products.
机构信息
Shanghai Key Laboratory of Green Chemistry and Chemical Process, School of Chemistry and Molecular Engineering, East China Normal University , 3663 North Zhongshan Road, Shanghai 200062, P. R. China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, P. R. China.
出版信息
Org Lett. 2017 Jun 16;19(12):3167-3170. doi: 10.1021/acs.orglett.7b01292. Epub 2017 Jun 1.
A uniformly strategic total synthesis of Aspidosperma alkaloids (+)-vincadifformine, (-)-quebrachamine, (+)-aspidospermidine, (-)-aspidospermine, (-)-pyrifolidine, and nine others from efficiently constructed tricyclic ketone 13 is reported. Highlights of these divergent and practical syntheses include (i) stereoselective intermolecular [4 + 2] cycloaddition to establish a C-E ring with one all-carbon quaternary stereocenter (C-5) and two bridged contiguous cis-stereocenters (C-12 and C-19), (ii) a Pd/C-catalyzed hydrogenation/deprotection/amidation cascade process to assemble the D ring, and (iii) Fischer indolization to forge the A-B ring.
从高效构建的三环酮 13 出发，我们报道了（+）-vincadifformine、（-）-quebrachamine、（+）-aspidospermidine、（-）-aspidospermine、（-）-pyrifolidine 以及其他九种 Aspidosperma 生物碱的统一战略全合成。这些发散性和实用性合成的亮点包括：（i）立体选择性的分子间[4+2]环加成反应，在 C-E 环上建立一个全碳季碳立体中心（C-5）和两个桥接的连续顺式立体中心（C-12 和 C-19）；（ii）Pd/C 催化的氢化/脱保护/酰胺化级联反应来组装 D 环；以及（iii）费歇尔吲哚化来构建 A-B 环。
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