醋酸锰(ⅲ促进的膦自由基与α,β-不饱和砜的反应研究及有机催化的不对称[4+3]环加成反应研究.pdf

醋酸锰(III)促进的膦自由基与α, β-不饱和砜的反应研究及有机催化的不对称[4+3]环加成反应研究 中文摘要 中文摘要 醋酸锰促进的自由基反应具有良好的区域选择性和立体选择性，并且反应条 件温和，已经成为有机合成化学中的一类重要方法。本文的第一部分主要研究了 醋酸锰促进的膦自由基与α, β-不饱和砜的反应，选择性地得到了烯基磷酸酯类化 合物，产率良好。 [4+3]环加成反应是构建七元环的一种有效的方法。近几年，不对称的[4+3]环 加成反应才有报道，但主要是基于手性辅基控制策略，仅有两例呋喃参与的催化 不对称[4+3]环加成反应。本文的第二部分研究了有机催化的不对称[4+3]环加成反 应构建双环[3.2.1]辛烷骨架，并且取得了初步结果。 产物的结构经核磁共振谱、质谱等得到了证实，部分结构通过 X 单晶衍射证实。 关键词：醋酸锰，自由基反应，α, β-不饱和砜，烯基磷酸酯，[4+3]环加成反 应，有机催化 作 者: 孙网彬 指导老师：邹建平 教授 孙炳峰 副研究员 I 英文摘要 醋酸锰(III)促进的膦自由基与α, β-不饱和砜的反应研究及有机催化的不对称[4+3]环加成反应研究 Studies on the Mn(OAc) Promoted Phosphonylation of α, 3 β -Unsaturated Sulfones and Asymmetric Organocatalytic [4 + 3] Cycloaddition Reactions Abstract Manganese(III) acetate promoted radical reactions have been important synthetic methods because of their high regio- and stereoselectivities as well as the mild reaction conditions. In the first part of this thesis, the reaction of phosphonyl radical and α, β -unsaturated sulfones promoted by Mn(OAc)3 were investigated in details. Various arylvinylphosphonates were obtained in good yields. The [4+3] cycloaddition reaction represents a powerful approach to the synthesis of seven-membered rings. It is only recently, however, the work on asymmetric [4 + 3] cycloaddition reactions has appeared in the literature. Almost all of the asymmetric approaches are based on a chiral auxiliary strategy, catalytic asymmetric [4 + 3] cycloaddition reactions are rarely known. The second part of the thesis, catalytic asymmetric [4 +