由立体硼酸烯基酯制备的烯基铜试剂。与烯丙基卤化物反应制备立体1,4-二烯的便捷途径

Narayan G. Bhat
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摘要

以原位生成的立体定向烯基铜为原料,进行了立体定向合成1,4-二烯的研究。用二溴硼烷-甲基硫醚配合物对炔烃进行硼氢化,然后用三甲基乙二醇处理,得到稳定的(E)-1-烯基硼酸酯。这些硼酸酯很容易与受阻碱(如叔丁酸钾)发生“盐”络合物。通过“ate”配合物将烯基从硼转金属到铜,保留了从开始的烯基硼酸酯定义的原始立体化学。研究了在溴甲基硫化铜的转金属反应中,代表性碱对立体硼烯基酯的影响以及这些硼酸酯随后的反应。原位生成的立体定义的烯基铜很容易与烯丙基溴偶联得到相应的1,4-二烯,并保留了立体化学性质。由于(Z)-1-烯基硼酸酯很容易获得,因此可以合成顺式和反式异构体1,4-二烯。
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Alkenylcopper Reagents Prepared from Stereodefined Alkenylboronate Esters. Reaction with Allylic Halides as a Convenient Route to Stereodefined 1,4-Dienes
The stereo-defined synthesis of 1,4-dienes based on in situ generated stereo-defined alkenylcopper reagents is presented. The hydroboration of alkynes with dibromoborane-methyl sulfide complex followed by treatment with trimethylene glycol provides stable (E)-1-alkenylboronate esters. These boronate esters readily undergo “ate” complexes with a hindered base such as potassium-tert.-butoxide. The transmetalation of the alkenyl group from boron to copper via the “ate” complexes retains the original stereochemistry defined from the starting alkenylboronate esters. The effect of representative bases on stereodefined alkenylboronate esters and subsequent reaction of these boronate esters in the transmetalation reaction with copper(I) bromidemethyl sulfide is investigated. The resulting stereo-defined alkenyl copper species generated in situ readily couple with allylic bromide to give the corresponding 1,4-dienes with retention of stereochemistry. Since (Z)-1-alkenylboronate esters are easily accessible, both cisand trans-isomeric 1,4-dienes are synthesized.
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