中国科学院上海化学研究所游书力团队最新提出通过Ir催化烯丙基脱芳构化反应合成双酚衍生物。相关论文于2020年11月3日发表在《美国化学会志》。

尽管具有多个立体定向中心的螺旋环己二烯酮在天然产物中经常被发现，但实现人工合成仍然十分困难。

在该研究中，研究人员通过Ir催化烯丙基脱芳基反应选择性地脱去甲基双酚衍生物的对称性，得到了具有三个连续立体中心的螺环环六二烯衍生物，产率高达90%，对映选择性好（高达99%ee）。反应时间短（30min）、催化剂用量少（低至0.2mol%）和在克级进行反应的能力证明了该反应的高效性。而(+)-tatanan B 和 (+)-tatanan C的全合成也需要以Ir催化烯丙基脱芳基反应作为关键步骤。

附：英文原文

Title: Enantioselective Desymmetrization of Bisphenol Derivatives via Ir-Catalyzed Allylic Dearomatization

Author: Ye Wang, Wen-Yun Zhang, Jia-Hao Xie, Zong-Lun Yu, Jia-Hao Tan, Chao Zheng, Xue-Long Hou, Shu-Li You

Issue&Volume: November 3, 2020

Abstract: Spirocyclic hexadienones with multiple stereogenic centers are frequently found in natural products but remain challenging targets to synthesize. Herein, we report the enantioselective desymmetrization of bisphenol derivatives via Ir-catalyzed allylic dearomatization reactions, affording spirocyclic hexadienone derivatives with up to three contiguous stereogenic centers in good yields (up to 90%) and excellent enantioselectivity (up to 99% ee). The high efficiency of this reaction is exemplified by the short reaction time (30 min), low catalyst loading (down to 0.2 mol %), and ability to perform the reaction on a gram-scale. The total syntheses of (+)-tatanan B and (+)-tatanan C were also realized using this Ir-catalyzed allylic dearomatization reaction as a key step.

DOI: 10.1021/jacs.0c09638

Source: https://pubs.acs.org/doi/10.1021/jacs.0c09638