环丁烯环的形成：烯丙基和亚乙烯基碳 - 碳双键在温和条件下的分子内[2 + 2]环加成反应。

Formation of a cyclobutylidene ring: intramolecular [2 + 2] cycloaddition of allyl and vinylidene C=C bonds under mild conditions.

作者信息

Alvarez Patricia, Lastra Elena, Gimeno José, Bassetti Mauro, Falvello Larry R

机构信息

Departamento de Química Orgánica e Inorgánica, Instituto de Química Organometálica Enrique Moles (Unidad Asociada al C.S.I.C.), Facultad de Química, Universidad de Oviedo, 33006 Oviedo, Spain.

出版信息

J Am Chem Soc. 2003 Mar 5;125(9):2386-7. doi: 10.1021/ja027209s.

DOI:10.1021/ja027209s

PMID:12603114

Abstract

Intramolecular [2 + 2] cycloaddition of two C=C bonds in vinylidene complexes [Ru(eta5-C9H7){=C=C(R)H}(PPh3){kappa1-(P)-PPh2(C3H5)][BF4] affords cyclobutylidene complexes [Ru(eta5-C9H7){kappa2-(P,C)-(=CC(R)HCH2CHCH2PPh2)}(PPh3)][BF4], which can be also obtained by reaction of terminal alkynes with [Ru(eta5-C9H7)(PPh3){kappa3-(P,C,C)-PPh2(C3H5)}][PF6]. The reaction proceeds under mild conditions via vinylidene complexes, and the activation parameters were determined by kinetic studies.

摘要

亚乙烯基配合物[Ru(η5-C9H7){=C=C(R)H}(PPh3){κ1-(P)-PPh2(C3H5)}][BF4]中两个C=C键的分子内[2 + 2]环加成反应生成环丁叉基配合物[Ru(η5-C9H7){κ2-(P,C)-(=CC(R)HCH2CHCH2PPh2)}(PPh3)][BF4]，该配合物也可通过末端炔烃与[Ru(η5-C9H7)(PPh3){κ3-(P,C,C)-PPh2(C3H5)}][PF6]反应得到。反应在温和条件下通过亚乙烯基配合物进行，并且通过动力学研究确定了活化参数。