TY - JOUR
T1 - 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
AU - Rei, Min‐Hon ‐H
AU - Chen, C. L.
AU - Liu, H. L.
PY - 1983/3
Y1 - 1983/3
N2 - Previous 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*)H of 1.67 Kcal/mol. With methyllithium, the ketone formed 77.5% of trans‐alcohol (D̊(D̊G*)D̊fs = 0.67 Kcal/mol). These data give a calculated D̊G* = 0.74 Kcal/mol which agrees well with the literature value of 0.87 or 0.28 Kcal/mol. Structural assignments of 2,2‐dimethyl‐4‐t‐butylyclohexanone, 1,2,2‐trimethyl‐cis‐ and trans‐4‐t‐butylcyclohexanols by pmr spectroscopic method are also given.
AB - Previous 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*)H of 1.67 Kcal/mol. With methyllithium, the ketone formed 77.5% of trans‐alcohol (D̊(D̊G*)D̊fs = 0.67 Kcal/mol). These data give a calculated D̊G* = 0.74 Kcal/mol which agrees well with the literature value of 0.87 or 0.28 Kcal/mol. Structural assignments of 2,2‐dimethyl‐4‐t‐butylyclohexanone, 1,2,2‐trimethyl‐cis‐ and trans‐4‐t‐butylcyclohexanols by pmr spectroscopic method are also given.
KW - 2,2‐Dimethyl‐4‐t‐Butylcyclohexanone Systems
KW - Stereochemistries
UR - http://www.scopus.com/inward/record.url?scp=84943500795&partnerID=8YFLogxK
U2 - 10.1002/jccs.198300001
DO - 10.1002/jccs.198300001
M3 - 文章
AN - SCOPUS:84943500795
SN - 0009-4536
VL - 30
SP - 1
EP - 9
JO - Journal of the Chinese Chemical Society
JF - Journal of the Chinese Chemical Society
IS - 1
ER -