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Highly Stereoselective Synthesis of Tetrasubstituted Acyclic All-Carbon Olefins via Enol Tosylation and Suzuki–Miyaura Coupling
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-07-26 00:00:00 , DOI: 10.1021/jacs.7b05071 Beryl X. Li 1 , Diane N. Le 1 , Kyle A. Mack 2 , Andrew McClory 1 , Ngiap-Kie Lim 1 , Theresa Cravillion 1 , Scott Savage 1 , Chong Han 1 , David B. Collum 2 , Haiming Zhang 1 , Francis Gosselin 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-07-26 00:00:00 , DOI: 10.1021/jacs.7b05071 Beryl X. Li 1 , Diane N. Le 1 , Kyle A. Mack 2 , Andrew McClory 1 , Ngiap-Kie Lim 1 , Theresa Cravillion 1 , Scott Savage 1 , Chong Han 1 , David B. Collum 2 , Haiming Zhang 1 , Francis Gosselin 1
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A highly stereocontrolled synthesis of tetrasubstituted acyclic all-carbon olefins has been developed via a stereoselective enolization and tosylate formation, followed by a palladium-catalyzed Suzuki–Miyaura cross-coupling of the tosylates and pinacol boronic esters in the presence of a Pd(OAc)2/RuPhos catalytic system. Both the enol tosylation and Suzuki–Miyaura coupling reactions tolerate an array of electronically and sterically diverse substituents and generate high yield and stereoselectivity of the olefin products. Judicious choice of substrate and coupling partner provides access to either the E- or Z-olefin with excellent yield and stereochemical fidelity. Olefin isomerization was observed during the Suzuki–Miyaura coupling. However, under the optimized cross-coupling reaction conditions, the isomerization was suppressed to <5% in most cases. Mechanistic probes indicate that the olefin isomerization occurs via an intermediate, possibly a zwitterionic palladium carbenoid species.
中文翻译：
烯醇甲苯磺酸化和铃木-宫浦偶联反应的高立体选择性合成四取代的无环全碳烯烃
通过立体选择性烯醇化和甲苯磺酸酯的形成，然后在Pd（OAc）存在下钯催化的甲苯磺酸酯和频哪醇硼酸酯的钯催化Suzuki-Miyaura交叉偶联，已经开发出了高度立体控制的四取代无环全碳烯烃合成方法。2 / RuPhos催化系统。烯醇甲苯磺酸化和Suzuki-Miyaura偶联反应都可以耐受一系列电子和空间上不同的取代基，并产生高收率和烯烃产物的立体选择性。基板和耦合伙伴的明智选择可提供对E-或Z的访问-烯烃具有优异的产率和立体化学保真度。在Suzuki-Miyaura偶联过程中观察到烯烃异构化。然而，在优化的交叉偶联反应条件下，大多数情况下异构化被抑制到<5％。机理探针表明，烯烃的异构化是通过中间体，可能是两性离子的钯类胡萝卜素发生的。
更新日期：2017-07-28
中文翻译：
烯醇甲苯磺酸化和铃木-宫浦偶联反应的高立体选择性合成四取代的无环全碳烯烃
通过立体选择性烯醇化和甲苯磺酸酯的形成，然后在Pd（OAc）存在下钯催化的甲苯磺酸酯和频哪醇硼酸酯的钯催化Suzuki-Miyaura交叉偶联，已经开发出了高度立体控制的四取代无环全碳烯烃合成方法。2 / RuPhos催化系统。烯醇甲苯磺酸化和Suzuki-Miyaura偶联反应都可以耐受一系列电子和空间上不同的取代基，并产生高收率和烯烃产物的立体选择性。基板和耦合伙伴的明智选择可提供对E-或Z的访问-烯烃具有优异的产率和立体化学保真度。在Suzuki-Miyaura偶联过程中观察到烯烃异构化。然而，在优化的交叉偶联反应条件下，大多数情况下异构化被抑制到<5％。机理探针表明，烯烃的异构化是通过中间体，可能是两性离子的钯类胡萝卜素发生的。
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