Chair and boat transition states for the Cope rearrangement. A CASSCF study
Chair and boat transition states for the Cope rearrangement. A CASSCF study
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用于 Cope 重新安排的椅子和船过渡状态。
DOI：
10.1021/ja00221a092
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发表时间：
1988
影响因子：
15
通讯作者：
D. Hrovat
中科院分区：
文献类型：
--
作者：
K. Morokuma;W. T. Borden;D. Hrovat
尽管人们普遍认为1,5 -己二烯的chair Cope重排通过具有C2h对称的物种，但该物种的几何形状和性质仍然存在争议。MINDO/23和MINDO/34计算均发现该物种为中间产物，两个烯丙基片段之间的键长R约为1.61 Á。最近的AMI计算给出了非c2 *过渡态的几何形状，与C2h中间体的几何形状非常接近，5表明Cope重排可能是协同反应，并且(1)(a)分子科学研究所，(b)华盛顿大学，(c)分子科学研究所访问科学家，1985。(2)综述：Gajewski， J. J.烃热异构化；学术：纽约，1981年；页166 - 76。(3) A. Komornicki；J. W. J.麦克弗。化学。《社会科学》，1997,8(5):453。(4)杜瓦，m.j.s.；福特，g.p.；麦基,毫升;热帕，H. S.；韦德，l.s.j.。化学。社会科学学报。1977,99,5069。
Although there is general agreement that the chair Cope re-arrangement of 1, 5-hexadiene passes through a species with C2h symmetry, 1 2 the geometry and nature of this species remain con-troversial. Both MINDO/23 and MINDO/34 calculations found this species to be an intermediate, with bond lengths, R, between the two allyl fragments of about 1.61 Á. More recent AMI calculations gave a geometry for the non-C2* transition state that was very close to that of the C2h intermediate, 5 suggesting the the Cope rearrangement might be a concerted reaction and that the (1)(a) Institute for Molecular Science,(b) University of Washington,(c) Visiting Scientist, Institute for Molecular Science, 1985.(2) Review: Gajewski, J. J. Hydrocarbon Thermal Isomerizations; Academic: New York, 1981; pp 166-76.(3) Komornicki, A.; Mclver, J. W. J. Am. Chem. Soc. 1976, 98, 4553.(4) Dewar, M. J. S.; Ford, G. P.; McKee, ML; Rzepa, H. S.; Wade, L. S. J. Am. Chem. Soc. 1977, 99, 5069.