2164-24-1Relevant academic research and scientific papers
The Rhodium Catalysed Direct Conversion of Phenols to Primary Cyclohexylamines
Tomkins, Patrick,Valgaeren, Carlot,Adriaensen, Koen,Cuypers, Thomas,Vos, Dirk E. De
, p. 3689 - 3693 (2018/07/31)
Cyclohexylamines are important intermediates in chemical industry, which are currently produced from petrochemical sources. Phenols, however, are an attractive sustainable feedstock. We here demonstrate the transformation of phenols with ammonia to primary cyclohexylamines. In contrast to previously reported chemistry which used palladium catalysts, we here show that rhodium is an excellent catalyst for the formation of primary cyclohexylamines. Different parameters were studied and it was shown that the reaction is applicable to a scope of phenolic compounds providing high selectivity.
Stereoselective Reductions of Substituted Cyclohexyl and Cyclopentyl Carbon-Nitrogen ? Systems with Hydride Reagents
Hutchins, Robert O.,Su, Wei-Yang,Sivakumar, Ramachandran,Cistone, Frank,Stercho, Yuriy P.
, p. 3412 - 3422 (2007/10/02)
Reductions of 3- and 4-substituted cyclohexyl imines, iminium salts, and enamines (via iminium ions) with various hydride reagents reveal that while small reagents (NaBH4, NaBH3CN) favor axial approach as observed with the corresponding ketones, even moderately bulky reagents (i.e., acetoxyboranes) attack preferentially from the equatorial side.This is in direct contrast to the results observed for the same reagents with the corresponding ketones and is interpreted as implying that additional steric interactions induced by the nitrogen substituents encumber axial attack by substituted hydride reagents and force approach from the equatorial direction.The very bulky tri-sec-butylborohydride anion affords highly stereodiscriminating equatorial attack.Reductions of 2-alkylcyclohexyl and 2-alkylcyclopentyl imines and enamines also proceed with high stereoselectivity to give cis-2-alkyl cyclic amines with both hindered and unhindered reagents.This is interpreted to be the result of (1) augmented steric interactions between nitrogen substituents and equatorial 2-alkyl groups (1,3-allylic strain) which induces conformational changes to favor the axial 2-alkyl conformer and (2) hindrance toward equatorial approach by reagents induced by axial alkyl substituents.The result is that equatorial approach is favored with equatorial 2-alkyl conformers and preferential axial approach with axial 2-alkyl conformers, leading to stereoselective production of cis-2-alkylamines. trans-2-n-Propyl-4-tert-butylcyclohexanone is reduced by LiBH(sec-Bu)3 preferentially from the axial direction in contrast to the usual highly selective equatorial attack observed with other cyclohexanones.
