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Diastereoselective Rhodium-Catalyzed [(3+2+2)] Carbocyclization Reactions with Tethered Alkynylidenecyclopropanes: Synthesis of the Tremulane Sesquiterpene Natural Products
Asian Journal of Organic Chemistry ( IF 2.8 ) Pub Date : 2020-12-20 , DOI: 10.1002/ajoc.202000482 P. Andrew Evans 1 , Molly J. Dushnicky 2 , Dasol Cho 3 , Jadab Majhi 2 , Seulhui Choi 3 , Bhavin V. Pipaliya 2 , Phillip A. Inglesby 4 , Mu-Hyun Baik 3
Asian Journal of Organic Chemistry ( IF 2.8 ) Pub Date : 2020-12-20 , DOI: 10.1002/ajoc.202000482 P. Andrew Evans 1 , Molly J. Dushnicky 2 , Dasol Cho 3 , Jadab Majhi 2 , Seulhui Choi 3 , Bhavin V. Pipaliya 2 , Phillip A. Inglesby 4 , Mu-Hyun Baik 3
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The development of a diastereoselective intramolecular rhodium-catalyzed [(3+2+2)] carbocyclization reactions of allyl ester-tethered alkynylidenecyclopropanes (ACPs) for the construction of the 5,7,5-tricyclic scaffold of the tremulane sesquiterpene natural products is described. This work illustrates that the stereoelectronic nature of the phosphite ligand is critical for attaining high levels of stereocontrol, which is supported by density functional theory (DFT) studies that indicate the migratory insertion step favors the formation of the cis-diastereoisomer. Consequently, several strategies were devised to access the thermodynamically more stable trans-diastereoisomer for the synthesis of the tremulanes; however, the attempts to either switch the sense of stereocontrol in the carbocyclization reaction or epimerize the C7 stereocenter of the cycloadduct provided only modest improvements. Hence, we elected to highlight the synthetic utility of this strategy with the development of concise and highly efficient syntheses of (±)-epi-tremulenolide A, (±)-epi-tremulenediol A and (±)-epi-ceriponol D.
中文翻译：
非对映选择性铑催化的 [(3+2+2)] 碳环化反应与系链亚炔基环丙烷：合成倍半萜烯天然产物
描述了非对映选择性分子内铑催化的 [(3+2+2)] 烯丙基酯系亚炔基环丙烷 (ACP) 碳环化反应的开发，用于构建 tremulane 倍半萜天然产物的 5,7,5-三环支架. 这项工作表明，亚磷酸酯配体的立体电子性质对于获得高水平的立体控制至关重要，密度泛函理论 (DFT) 研究表明，迁移插入步骤有利于顺式非对映异构体的形成。因此，设计了几种策略来获得热力学上更稳定的反式-用于合成颤音的非对映异构体；然而，改变碳环化反应中立体控制的意义或差向异构化环加合物的 C7 立体中心的尝试仅提供了适度的改进。因此，我们决定强调这一战略的综合效用与简洁的开发和（±）的高效合成-外延-tremulenolide A，（±） -外延-tremulenediol A和（±） -外延-ceriponol D.
更新日期：2020-12-20
中文翻译：
非对映选择性铑催化的 [(3+2+2)] 碳环化反应与系链亚炔基环丙烷：合成倍半萜烯天然产物
描述了非对映选择性分子内铑催化的 [(3+2+2)] 烯丙基酯系亚炔基环丙烷 (ACP) 碳环化反应的开发，用于构建 tremulane 倍半萜天然产物的 5,7,5-三环支架. 这项工作表明，亚磷酸酯配体的立体电子性质对于获得高水平的立体控制至关重要，密度泛函理论 (DFT) 研究表明，迁移插入步骤有利于顺式非对映异构体的形成。因此，设计了几种策略来获得热力学上更稳定的反式-用于合成颤音的非对映异构体；然而，改变碳环化反应中立体控制的意义或差向异构化环加合物的 C7 立体中心的尝试仅提供了适度的改进。因此，我们决定强调这一战略的综合效用与简洁的开发和（±）的高效合成-外延-tremulenolide A，（±） -外延-tremulenediol A和（±） -外延-ceriponol D.
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