Shenzhen Grubbs Institute, Department of Chemistry, Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, China.
J Am Chem Soc. 2020 Nov 25;142(47):19868-19873. doi: 10.1021/jacs.0c10116. Epub 2020 Nov 11.
The first and asymmetric total synthesis of 4β-acetoxyprobotryane-9β,15α-diol, containing a rare and highly strained -fused bicyclo[3.3.0]octane ring system, has been achieved. The synthetically challenging [6-5-5] tricyclic ring system in the final product was efficiently and diastereoselectively synthesized via an asymmetric rhodium-catalyzed [4 + 2] cycloaddition reaction, followed by a unique benzilic acid type rearrangement under very mild conditions. The seven contiguous stereocenters were installed efficiently and diastereoselectively.
首次不对称全合成了含有罕见的高度张力 - 稠合双环[3.3.0]辛烷环系的 4β-乙酰氧基普罗托兰烷-9β,15α-二醇。在最终产物中具有合成挑战性的[6-5-5]三环体系通过不对称铑催化的[4 + 2]环加成反应有效地和立体选择性地合成，然后在非常温和的条件下进行独特的苯偶姻型重排。七个连续的立体中心被有效地和立体选择性地安装。
