The elimination of lithium, magnesium and aluminium enolatea of isobutyrates of medium ring cyclanols occurs in a syn fashion. A set of experimental procedures is presented. This elimination seems to be restricted to strained systems. The stereo-chemistry has been determined on stereospecifically deuterated cyclooctanol isobutyrates. The primary isotope effect kH/k2 was 3.0 ± 0.1 and the secondary
中环环醇的异丁酸酯的锂,镁和铝烯醇盐的消除以同步方式发生。提出了一组实验程序。这种消除似乎仅限于紧张的系统。立体化学已经在立体特异性氘化的环辛醇异丁酸酯上确定。一级同位素效应k H / k 2为3.0±0.1,二级同位素效应为1.1。为此同步消除和相关消除建议使用名称“β'β消除”。
ACID-CATALYZED EQUILIBRATIONS OF ENDOCYCLIC AND EXOCYCLIC OLEFINS
作者:Arthur C. Cope、Dieter Ambros、Engelbert Ciganek、Charles F. Howell、Zenon Jacura
DOI:10.1021/ja01521a068
日期:1959.6
Mechanisms of elimination reactions. XXI. Ring-size effects and the nature of the excited states in the photolysis of cycloalkyl phenylacetates
作者:Michael L. Yarchak、J. Christopher. Dalton、William H. Saunders
DOI:10.1021/ja00797a022
日期:1973.8
η<sup>3</sup>-Allylpalladium Complexes from Medium-Ring Cycloalkenes
作者:Jean-Marie Rosset、Matthew P. Glenn、John D. Cotton、Anthony C. Willis、Colin H. L. Kennard、Karl A. Byriel、Bruce H. Riches、William Kitching
DOI:10.1021/om971132c
日期:1998.5.1
The dimeric eta(3)-allylpalladium chloride complexes formed from various cycloalkenes (C-7-C-13) and some methyl-and tert-butyl-substituted cycle alkenes have be en characterized by H-1 and C-13 NMR spectroscopy and in selected cases by X-ray crystallography. The formation of syn and anti isomers in the larger ring systems is demonstrated, and complexes with a rearranged ring system are formed from tert-butylcyclodecene and tert-butylcyclododecene. The sesquiterpene, carophyllene, is shown to form an eta(3)-allyl exocyclic complex, exclusively from the (E)-double bond. Cis and trans isomers, with respect to allyl group orientation in these halo-bridged dimers, have been identified by low-temperature (190K) NMR spectroscopy, and their interconversion (Delta G(double dagger) approximate to 11 kcal/mol) is considered to involve a "cubic" eta(3)-allylpalladium chloride tetramer.
Thermal cycloelimination of bis(dialkylamino)cyclopropanes to amidines and cycloalkenes