Generation of Organo Copper Species in Organotin/Coppter (I) Systems and Application to Carbon-Carbon Bond Formation

研究了有机锡/氯化铜体系中有机铜物种的生成及其在新的碳-碳键形成中的应用。烯基锡/氯化铜/NMP体系中烯基铜（I）物种的生成和反应可能分别为3-烯基-Δ ^3-头孢烯和3-烯基-Δ ^2-头孢烯开辟新的合成路线。联吡啶或三联吡啶的存在下，在反应介质中稳定的铜物种有效地促进3-氯甲基头孢烯的烯基化。在联吡啶或三联吡啶存在下，烯丙基或苄基卤与铜粉在NMP中直接反应可生成类似的铜（I）物种。利用原位生成的铜物种成功地实现了3-氯甲基头孢烯的同偶联和异偶联，并研究了氢化锡和氯化铜在NMP中的结合，其中形成了配位不饱和的氢化铜物种.原位生成的氢化铜（I）与丙二烯羧酸酯、烯基三氟甲磺酸酯和烯丙基卤化物的反应顺利进行，提供了3-去甲头孢烯、其Δ ^2-异构体和3-外-亚甲基头孢烯的新合成方案。本研究创新的有机铜物种与传统方法制备的有机铜物种有很大不同。有机铜物种的进一步应用正在进行中。

Generation of organocopper species in organotin/copper (I) chloride systems and applicatoins t to new carbon-carbon bond formaiton have been investigated. The generation and reaction of alkenylcopper (I) species in alkenyltins/copper (I) chloride/NMP systems could open new synthetic routes to 3-alkenyl-DELTA^3-cephems and 3-alkenyl-DELTA^2-cephems, respectively. The presence of bipyridine or terpyridine in the reaction media stabilized the copper species effectively to promote alkenylation of 3-chloromethylcephem. Similar copper (I) species could be generated by direct reaction of allylic or benzylic halides with copper powder in NMP in the presence of bipyridine or terpyridine. Homocoupling and heterocoupling of 3-chloromethyl-cephem were successfully achieved by use of the in situ generated copper species.A combination of tin hydride and copper (I) chloride in NMP was also investigated, in which, coordinatively unsaturated copper (I) hydride species were formed. Reaction of the in situ generated copper (I) hydride with allenecarboxylate, alkenyl triflate, and allylic halides proceeded smoothly to offer new synthetic schemes of 3-norcephem, its DELTA^2-isomer, and 3-exo-methylenecepham. The organocopper species innovated in this research project are far different from those preapred by the conventional methods. Further applications of the organocopper species are now in progress.