碳正离子环化反应中类碳鎓离子过渡态几何结构——桥连相关应变如何影响5-6选择性。
Carbonium carbenium ion-like transition state geometries for carbocation cyclization - how strain associated with bridging affects 5- 6- selectivity.
作者信息
Gutierrez Osvaldo, Harrison Jason G, Felix Ryan J, Guzman Fernando Cortés, Gagné Michel R, Tantillo Dean J
机构信息
Department of Chemistry, University of California-Davis, 1 Shields Avenue, Davis, CA 95616, USA.
Department of Chemistry, University of North Carolina at Chapel Hill, North Carolina 27599-3190, USA.
出版信息
Chem Sci. 2013 Oct;4(10). doi: 10.1039/C3SC51657A.
Abstract
Quantum chemical calculations are used to explore the origins of regioselectivity for proton-, Pt(II)- and Pd(II)-promoted cyclizations of 1,5-hexadienes, 5-aminoalkenes, and allylic acetimidates. The strain associated with achieving carbonium ion-like transition state geometries is shown to be a key factor in controlling 5- 6- selectivity.
摘要
量子化学计算用于探究质子、Pt(II) 和 Pd(II) 促进的 1,5 - 己二烯、5 - 氨基烯烃及烯丙基乙酰亚胺酯环化反应区域选择性的起源。结果表明，与形成类碳正离子过渡态几何结构相关的张力是控制 5 - 6 选择性的关键因素。
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2
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Org Lett. 2011 Nov 4;13(21):5893-5. doi: 10.1021/ol202621g. Epub 2011 Oct 12.
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