NEIGHBORING BORON IN NUCLEOPHILIC DISPLACEMENT
NEIGHBORING BORON IN NUCLEOPHILIC DISPLACEMENT
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DOI：
10.1021/ja00900a017
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发表时间：
1963-01-01
影响因子：
15
通讯作者：
MAH, RWH
中科院分区：
文献类型：
--
作者：
MATTESON, DS;MAH, RWH
卤代烷基硼酸二丁酯L-溴-3，3，3-三氯丙烷-3，3-三氯丙烷-硼酸二丁酯与碘、丁醚、丁硫基等亲核试剂的取代反应，极大地促进了邻位硼原子的作用。丁醚显然首先攻击硼原子，形成四价硼阴离子，然后随着溴离子的排出而重新排列。B-芳基和B-烷基-B-(L-溴-3，3，3-三氯-L-丙基)-硼酸丁酯的行为为这一机理提供了强有力的支持，它在温和的碱处理下释放出溴离子，使B-芳基或B-烷基从硼迁移到碳。
Displacement of bromide ion from the-haloalkaneboronic ester, dibutyl l-bromo-3, 3, 3-trichloropropane-lboronate, by nucleophilessuch as iodide, butoxide, and butyl mercaptide ion is greatly facilitated by the neighboring boron atom. Butoxide evidently attacks the boron atom first to form the tetracovalent boron anion, which then rearranges with expulsion of bromide ion. Strong support for this mechanism is furnished by the behavior of butyl B-aryl-and B-alkyl-B-(l-bromo-3, 3, 3-trichloro-l-propyl)-borinates, which upon mild base treatment expel bromide ion ivith migration of the B-aryl or B-alkyl group from boron to carbon.