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Stereochemistry of the Reactions of Cyclic Ketones with Lithium Aluminum Hydride and Methyllithium. IV. The Stereochemistry of the Reactions in 2,2‐Dimethyl‐4‐t‐Butylcyclohexanone Systems

 

作者: Min‐Hon Rei,   C. L. Chen,   H. L. Liu,  

 

期刊: Journal of the Chinese Chemical Society  (WILEY Available online 1983)
卷期: Volume 30, issue 1  

页码: 1-9

 

ISSN:0009-4536

 

年代: 1983

 

DOI:10.1002/jccs.198300001

 

出版商: WILEY‐VCH Verlag

 

关键词: Stereochemistries;2,2‐Dimethyl‐4‐t‐Butylcyclohexanone Systems

 

数据来源: WILEY

 

摘要:

AbstractPrevious publication showed that the stereochemistry of lithium aluminum hydride reduction of cyclic ketones can be evaluated by the use of an empirical equation, . This paper reports further test of this relationship in the new system of 2,2‐dimethyl‐4‐t‐butyl‐cyclohexanone.Lithium aluminum hydride reduction of this ketone yields 95.6%trans‐alcohol (lit., 95.9%) corresponding to D̊(D̊G*)Hof 1.67Kcal/mol. With methyllithium, the ketone formed 77.5% oftrans‐alcohol (D̊(D̊G*)D̊fs= 0.67Kcal/mol). These data give a calculatedD̊G* = 0.74Kcal/molwhich agrees well with the literature value of 0.87 or 0.28Kcal/mol.Structural assignments of 2,2‐dimethyl‐4‐t‐butylyclohexanone, 1,2,2‐trimethyl‐cis‐ andtrans‐4‐t‐butylcyclohexanols by

 

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