3211-27-6Relevant articles and documents
Hydrogen shifts in cyclohexylcarbenes. Spatial dependence of activating power and of primary deuterium isotope effects
Kenar, James A.,Nickon, Alex
, p. 14871 - 14894 (2007/10/03)
The conformationally biased ketones 4-t-butyl-cis-2-methylcyclohexanone (1c) and 4-t-butyl-cis-2-trans-6-dimethylcyclohexanone (7a; and its 2,6-dideuterio derivative 7c) were converted into p-toluenesulfonylhydrazone Li salts. Thermolysis or photolysis generated putative singlet carbenes, which underwent competitive axial vs equatorial H shift (or D shift in the case of 7c) to give alkenes. Product analysis showed that a bystander Me(eq) substituent promotes a geminal H shift several times more efficiently than does a bystander Me(ax). This geometry-dependent activating power parallels behavior noted earlier for OMe and Ph bystander groups; but as Me groups are rotationally symmetric and possess no lone pair or π electrons this phenomenon cannot be attributed solely to rotameric considerations or to effects involving mobile electron clouds. For the trans-dimethylcarbenes 10a and 10c the primary deuterium isotope effect (k(H)/k(D)) for axial migration (I(ax)) was determined to be ca. 1.5 times larger than that for equatorial migration (I(eq)). This finding invalidates the common assumption that I(ax) = I(eq) and suggests that published data on deuterium isotope effects and on H(ax)/H(eq) migration selectivities need to be adjusted.
Activation of Reducing Agents. Sodium Hydride Containing Complex Reducing Agents. 36. Stereoselective Reduction of Alkylcyclohexanones and Rigid Ketones by MCRA's
Fort, Yves,Feghouli, Abdelhafid,Vanderesse, Regis,Caubere, Paul
, p. 5911 - 5915 (2007/10/02)
The stereoselectivity of reduction of selected ketones by a variety of Complex Reducing Agents (resulting from the Aggregative Activation of NaH and symbolized MCRA's) has been investigated.The stereochemistry of reduction is shown to be dependent on the nature of the metal.Steric hindrance plays an important role and the apparent size of the reagents follows the trend MnCRA's > ZnCRA's, CdCRA's > NiCRA's, CoCRA's.On the other hand NiCRA's and CoCRA's have been found as very strong isomerizing reagents.Insertion of the metal species into the C-O bond with formation of metallacycles appears as one of the possible mechanisms intervening during the reduction of ketones by MCRA's.
Stereochemistry of Nucleophilic Reductions of 2-Methyl-4-t-butylcyclohexanones. Further Support for the Linear Combination of SSC and PSC Stereochemical Models
Fang, Jim-Min,Sun, Shih-Feng,Rei, Min-Hon
, p. 747 - 750 (2007/10/02)
trans-2-Methyl-4-t-butylcyclohexanone reacts with lithium aluminum hydride, lithium trimethoxyaluminium hydride and methyl-lithium with equal stereoselectivity of axial attack (i. e. 95 +/- 1 percent).This is attributed to the equal steric strain control