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Beyond geminal diesters: increasing the scope of metal-mediated vinylcyclopropane annulations while decreasing pre-activation
Organic & Biomolecular Chemistry ( IF 2.9 ) Pub Date : 2018-04-11 00:00:00 , DOI: 10.1039/c8ob00593a Duncan K. Brownsey 1, 2, 3, 4 , Evgueni Gorobets 1, 2, 3, 4 , Darren J. Derksen 1, 2, 3, 4
Organic & Biomolecular Chemistry ( IF 2.9 ) Pub Date : 2018-04-11 00:00:00 , DOI: 10.1039/c8ob00593a Duncan K. Brownsey 1, 2, 3, 4 , Evgueni Gorobets 1, 2, 3, 4 , Darren J. Derksen 1, 2, 3, 4
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The utilization of unactivated substrates in annulation reactions provides access to complex products without the need for subsequent removal of the activating group. Vinylcyclopropanes (VCPs), occurring naturally in several monoterpene natural products, are an important building block for organic chemistry, and can be activated by electron withdrawing substituents directly on the cyclopropane to facilitate ring opening reactions. However, many VCPs that lack these activated groups remain reactive with several group 8, 9 and 10 transition metals, by alternative modes of activation, forming metallacycles. These useful intermediates produce annulation products in reactions with unsaturated π-units, providing rapid access to new carbocycles. Several formal cycloadditions that incorporate unactivated VCPs as substrates have been developed, including [5 + 2], [5 + 2 + 1], [5 + 1 + 2 + 1], [3 + 2], [3 + 2 + 1], [5 + 1], and others, using Rh, Ni, Ru, Ir, Fe and Co based catalysts. Mono- and polycyclic ring systems have been made using these methods with their utility demonstrated through the synthesis of complex natural products. This review will summarize the annulations of VCPs that lack geminal diesters, but retain reactivity via transition metal catalysts.
中文翻译：
超越双酯二酯：增加金属介导的乙烯基环丙烷环化的范围，同时减少预活化
在环化反应中未活化底物的利用提供了获得复杂产物的途径，而无需随后除去活化基团。天然存在于几种单萜天然产物中的乙烯基环丙烷（VCP）是有机化学的重要组成部分，可以通过直接在环丙烷上吸电子的取代基进行活化以促进开环反应。但是，许多缺少这些活化基团的VCP通过替代活化方式仍可与几种8、9和10型过渡金属发生反应，形成金属环。这些有用的中间体在与不饱和π-单元的反应中产生环状产物，可快速获得新的碳环化合物。已经开发了几种将未活化的VCP作为底物的正式环加成物，包括[5 + 2]，[5 + 2 +1]，[5 +1 + 2 +1]，[3 + 2]，[3 + 2 +1]，[5 +1]等，使用Rh ，Ni，Ru，Ir，Fe和Co基催化剂。已经使用这些方法制备了单环和多环系统，并通过合成复杂的天然产物证明了它们的效用。这篇综述将总结缺乏双链二酯但保留反应性的VCP的环状结构通过过渡金属催化剂。
更新日期：2018-04-11
中文翻译：
超越双酯二酯：增加金属介导的乙烯基环丙烷环化的范围，同时减少预活化
在环化反应中未活化底物的利用提供了获得复杂产物的途径，而无需随后除去活化基团。天然存在于几种单萜天然产物中的乙烯基环丙烷（VCP）是有机化学的重要组成部分，可以通过直接在环丙烷上吸电子的取代基进行活化以促进开环反应。但是，许多缺少这些活化基团的VCP通过替代活化方式仍可与几种8、9和10型过渡金属发生反应，形成金属环。这些有用的中间体在与不饱和π-单元的反应中产生环状产物，可快速获得新的碳环化合物。已经开发了几种将未活化的VCP作为底物的正式环加成物，包括[5 + 2]，[5 + 2 +1]，[5 +1 + 2 +1]，[3 + 2]，[3 + 2 +1]，[5 +1]等，使用Rh ，Ni，Ru，Ir，Fe和Co基催化剂。已经使用这些方法制备了单环和多环系统，并通过合成复杂的天然产物证明了它们的效用。这篇综述将总结缺乏双链二酯但保留反应性的VCP的环状结构通过过渡金属催化剂。
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