[3 + 2]-Cyclopentane annulation reactions using organoiron reagents
[3 + 2]-Cyclopentane annulation reactions using organoiron reagents
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使用有机铁试剂的 [3 2]-环戊烷成环反应
DOI：
10.1021/om00072a025
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发表时间：
1982
期刊：
影响因子：
--
通讯作者：
M. Rosenblum
中科院分区：
文献类型：
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作者：
A. Bucheister;P. Klemarczyk;M. Rosenblum
有机铁配合物1中的烯丙基配体（r-烯丙基OFp [Fp=（71 2345-C5 H5）Fe（CO）2]）在溴化铝催化下与环己烯酮以及自身与2-乙氧羰基环烯酮的反应中作为C3偶极合成子，得到环戊烷环合产物。这些反应中烯酮和有机金属试剂的取代反应的结构限制已被研究。炔属配体（？; 1-2-丁炔基）Fp类似地使溴化铝催化的与环己烯酮的[3+ 2]环加成反应不足，[4+ 2]环加成反应广泛用于碳环和杂环的六元环体系的构建，并且许多相关的杂偶极试剂可用于通过[4+ 2]环加成反应合成五元杂环。4+ 1] 1或[3+ 2] 2环加成反应，用于构建环戊烷环的类似合成子较难获得。3在后一种试剂中，二羰基[5-（3-烯丙基）氟]配合物，如1及其同系物，已被证明表现为1，3偶极子
The allyl ligand in the organoiron complex 1,(r^-allyOFp [Fp=(71 2345-C5Hs) Fe (CO) 2], serves as a C3 dipolar synthon in aluminum bromide catalyzed reactions with cyclohexenone andby itself with 2-carbethoxy-cycloalkenones, affording cyclopentane annulation products. The structural limitations of these reactions with respect tosubstitution of the enone and the organometallic reagent have been examined. The acetylenic ligand in (?; 1-2-butynyl) Fp similarly underdoes aluminum bromide catalyzed [3+ 2] cycloaddition reaction with cyclohexenone, but (jjM-propynyflFp yields instead the product of [2+ 2] cycloaddition.While [4+ 2] cycloadditions serve widely for the con-struction of carbocyclic and heterocyclic1 6-membered ring systems and a number of related hetero dipolar reagents are available for the synthesis of 5-membered heterocycles by [4+ l] 1 or [3+ 2] 2 cycloaddition reactions, analogous synthons for the construction of cyclopentane rings are less accessible. 3 Among the latter reagents, dicarbonyl [5-cyclopentadienyl)(t^-allyfliron complexes, such as 1 and its congeners, have been shown to behave as 1, 3 dipoles