亲电加成机理,立体特殊性和区域选择性的轨道控制规则(英文)

• 作 者: 戴乾圜 施美德
• 机 构: Beijing Polytechnic University,University of Toronto,
• 出 处: 北京工业大学学报
• 发表日期: 1986年02期
• 关键词: 区域选择性 特殊性 亲电加成 分子轨道理论 亲电加成反应 加成 原子 桥型 控制规则 机理

本文根据定性分子轨道理论,提出了适用于大多数亲电加成反应的普遍性理论规则,即以周期表四、五周期原子为亲电中心的加成,通常为桥型离子加成机理,具反式立体特殊性和非区域选择性。第一、二周期原子为加成中心者,通常为开放离子机理,本质上为非立体特殊性和区域选择性;三及六周期原子为中心者,易受+I及+M影响,而转化为开放离子的桥型离子机理和相应的易逆转的反式立体特殊性和易逆转的非区域选择性。

Based on the theory of qualitative molecular orbital, this paper presents the universal theory rules applicable to most electrophilic addition reactions, that is, the addition of four or five periodic atoms to the electrophilic centers is usually the bridge-type ion addition mechanism, A trans-dimensional and non-regional specificity. The first and second cycle atoms are the addition centers, usually open-ion mechanism, which is non-stereoselective and regio-selective in nature. The three- and six-cycle atomic centers are susceptible to + I and + M, Is a bridged ion mechanism for open ions and the corresponding reversible stereospecificity and reversible non-regioselectivity.