Cobalt-Catalyzed 1,4-Hydrobutadienylation of 1-Aryl-1,3-dienes with 2,3-Dimethyl-1,3-butadiene
Cobalt-Catalyzed 1,4-Hydrobutadienylation of 1-Aryl-1,3-dienes with 2,3-Dimethyl-1,3-butadiene
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DOI：
10.1002/anie.201103613
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发表时间：
2011-01-01
影响因子：
16.6
通讯作者：
Schmalz, Hans-Guenther
中科院分区：
文献类型：
--
作者：
Bohn, Martin A.;Schmidt, Anastasia;Schmalz, Hans-Guenther
除了简单的交叉偶联之外，钴基催化剂在构建新的碳-碳键方面的应用越来越引起人们的兴趣，并为广泛的产品开辟了途径cobr2 -配体- zn - zni2体系已被确定为不饱和有机分子可控和原子经济转化的多功能预催化剂。由这种迷人的过渡金属促进的两大类反应因起始材料和配体的不同而不同（方案1）。第一类涉及炔的转化，如内炔与末端烯烃之间的醛烯反应(A)，内炔与环戊烯之间的[2+ 2]环加成反应(B)，[3]和[2+ 2+ 2]炔的三聚化反应(C)第二类是基于1,3 -丁二烯基序的反应。这些反应是炔烃和1,3 -二烯的Diels-Alder反应（准选择性或间选择性）(D)，[5][4+ 2+ 2]环加成得到八元环(E)，[6]和1,4 -氢乙烯化反应[7]，从1,3 -二烯开始得到1,4 -二烯和末端烯烃(F)。钴催化的1,4 -氢乙烯化反应是对铁基转化的补充，铁基转化产生相应的线性1,4 -氢乙烯化产物
The application of cobalt-based catalysts for the construction of new carbon–carbon bonds, beyond simple cross-coupling, is of increasing interest and opens access to a wide range of products.[1] The CoBr2-ligand-Zn-ZnI2 system has been identified as a versatile precatalyst for the controlled and atomeconomical transformation of unsaturated organic molecules. Two broad classes of reactions, which are promoted by this fascinating transition metal and differ by the starting materials and ligands, are discernable (Scheme 1). The first class concerns transformations of alkynes such as the Alder-ene reaction between internal alkynes and terminal olefins (A),[2] the [2+ 2] cycloaddition between internal alkynes and cyclopentene (B),[3] and the [2+ 2+ 2] trimerization of alkynes (C).[4] The second class involves reactions based upon the 1, 3-butadiene motif. These reactions are the Diels–Alder reaction (a para-or meta-selective version) of alkynes and 1, 3-dienes (D),[5] the [4+ 2+ 2] cycloaddition leading to eight-membered rings (E),[6] and the 1, 4-hydrovinylation reaction,[7] which leads to 1, 4-dienes starting from 1, 3-dienes and terminal olefins (F). The cobalt-catalyzed 1, 4-hydrovinylation reaction is complementary to an iron-based transformation which delivers the corresponding linear 1, 4-hydrovinylation products.[8]