PALLADIUM-CATALYZED INTERMOLECULAR AND INTRAMOLECULAR CROSS-COUPLING REACTIONS OF B-ALKYL-9-BORABICYCLO[3.3.1]NONANE DERIVATIVES WITH 1-HALO-1-ALKENES OR HALOARENES - SYNTHESES OF FUNCTIONALIZED ALKENES, ARENES, AND CYCLOALKENES VIA A HYDROBORATION COUPLING SEQUENCE
PALLADIUM-CATALYZED INTERMOLECULAR AND INTRAMOLECULAR CROSS-COUPLING REACTIONS OF B-ALKYL-9-BORABICYCLO[3.3.1]NONANE DERIVATIVES WITH 1-HALO-1-ALKENES OR HALOARENES - SYNTHESES OF FUNCTIONALIZED ALKENES, ARENES, AND CYCLOALKENES VIA A HYDROBORATION COUPLING SEQUENCE
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DOI：
10.1021/ja00183a048
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发表时间：
1989-01-04
影响因子：
15
通讯作者：
SUZUKI, A
中科院分区：
文献类型：
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作者：
MIYAURA, N;ISHIYAMA, T;SUZUKI, A
b -烷基-9-硼比环的交叉偶联反应[3.3]。[1]壬烷（BR-9-BBN），很容易从烯烃中通过硼化氢得到，在催化量的PdCl2 （dppf）和碱（如氢氧化钠、碳酸钾和磷酸盐）的存在下，与1-卤-1-烯烃或卤代芳烃形成相应的烯烃或芳烃。由于反应对任何偶联体上的各种官能团都是耐受的，因此在温和的条件下可以得到立体化学上纯官能团化的烯烃和芳烃。该反应的实用性通过立体选择性合成1,5 -烷烯（7和8）和类固醇侧链的延伸（11）得到证明。卤代烷的硼化氢（12），然后是分子内交叉偶联，形成了一个短步骤合成环烯烃、苯并融合环烯烃和外环烯烃（14和16）的过程。
The cross-coupling reaction of B-alkyl-9-borabicyclo [3.3. 1] nonanes (BR-9-BBN), readily obtainable from alkenes by hydroboration, with 1-halo-1-alkenes or haloarenes in the presence of a catalytic amount of PdCl2 (dppf) and bases, such as sodium hydroxide, potassium carbonate, and phosphate, gave the corresponding alkenes or arenes. Because thereaction is tolerant of a variety of functionalities on either coupling partner, stereochemically pure functionalized alkenes and arenes can be obtained undermild conditions. The utility of the reaction was demonstrated by the stereoselective synthesis of 1, 5-alkadienes (7 and 8) and the extension of a side chain in a steroid (11). The hydroboration of haloalkadienes (12), followed by the intramolecular cross-coupling, gave a short-step procedure for synthesis of cycloalkenes, benzo-fused cycloalkenes, and exocyclic alkenes (14 and 16).