TOWARD MOLECULAR MAGNETS - THE METAL-RADICAL APPROACH
TOWARD MOLECULAR MAGNETS - THE METAL-RADICAL APPROACH
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DOI：
10.1021/ar00167a004
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发表时间：
1989-11-01
影响因子：
18.3
通讯作者：
REY, P
中科院分区：
文献类型：
--
作者：
CANESCHI, A;GATTESCHI, D;REY, P
结论溶液中酰基转移反应不应仅以加成或缔合中间体为反应机理。在讨论亲核试剂间酰基转移的机理时，除了考虑解离和缔合途径的分步机理外，还应考虑协同机理。强碱性给体亲核试剂和受体亲核试剂倾向于“紧”过渡态，而弱碱性亲核试剂则倾向于“开”或解离过渡态。酰基转移的协调机制在所有酸的衍生物中比以前假设的更常见。
ConclusionsAcyl group transfer reactions in solution should not be assumed to involve only addition or associative in-termediates in their mechanisms. Discussion of mech-anism for transferof acyl groups between nucleophiles should seriously consider the concerted pathway as well as the stepwise mechanisms following dissociative and associative routes. Strongly basic donor and acceptor nucleophiles favor “tight” transition states whereas weakly basic nucleophiles encourage “open” or disso-ciative transition states. Concerted mechanisms of acyl group transfer are more common among derivatives of all acids than was previously supposed.