吡咯烷催化环戊二烯与α,β-不饱和羰基化合物的反应：1,2-加成与1,4-加成
Pyrrolidine catalyzed reactions of cyclopentadiene with α,β-unsaturated carbonyl compounds: 1,2- versus 1,4-additions.
作者信息
Coskun Necdet, Çetin Meliha, Gronert Scott, Ma Jingxiang, Erden Ihsan
机构信息
On leave from Uludag University, Department of Chemistry, 16059 Bursa-Turkey.
Department of Chemistry, Virginia Commonwealth University, 1001 West Main Street, Richmond, Virginia, 2384, Oliver Hall 3041.
出版信息
Tetrahedron. 2015 May 6;71(18):2636-2642. doi: 10.1016/j.tet.2015.03.042.
Abstract
A systematic study of the reactions of cyclopentadiene with α,β-unsaturated carbonyl compounds in the presence of catalytic pyrrolidine-HO revealed that the reactions can either proceed with a Michael attack at the β-carbon of enone, or 1,2-addition to the carbonyl, leadingeither to 4-cyclopentadienyl-2-butanones or 6-vinylfulvenes. The former can be isolated and/or converted to the corresponding 1,2-dihydropentalenes with base (or in one-pot at longer reaction times). Substitution pattern on the enones on the competing pathways have been studied and consistent mechanisms are proposed.
摘要
对环戊二烯与α,β-不饱和羰基化合物在催化量吡咯烷-HO存在下的反应进行的系统研究表明，反应既可以通过对烯酮β-碳的迈克尔加成进行，也可以对羰基进行1,2-加成，分别生成4-环戊二烯基-2-丁酮或6-乙烯基富烯。前者可以分离出来，和/或用碱转化为相应的1,2-二氢并五苯（或在较长反应时间下单釜反应）。研究了竞争途径中烯酮上的取代模式，并提出了一致的反应机理。
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