192195-22-5Relevant academic research and scientific papers
Probing the mechanism of the anomalous intramolecular C-H insertion reaction of rhodium carbenoids by analysis of kinetic isotope effects
Clark,Wong, Yung-Sing,Townsend, Robert J
, p. 6187 - 6190 (2001)
The mechanism of the anomalous intramolecular insertion reaction of a rhodium carbenoid into an ethereal C-H bond has been explored using deuterium labelled substrates. Comparison of primary kinetic isotope effects and analysis of ratios of diastereoisome
Asymmetric synthesis of secondary alcohols from primary alcohols via intramolecular carbenoid C-H insertion catalyzed by rhodium(II) 3-phenylcholestane-2-carboxylate
Hwang, Cheol Hee,Chong, You Hoon,Song, Sue Yeon,Kwak, Hyo Shin,Lee, Eun
, p. 816 - 817 (2007/10/03)
Chiral secondary alcohols may be prepared from primary alcohols via asymmetric C-H insertion reactions of α′-alkoxy-α-diazoketones catalyzed by rhodium(II) (2R,3K)-3-phenylcholestane-2-carboxylate.
Anomalous intramolecular C-H insertion reactions of rhodium carbenoids: Factors influencing the reaction course and mechanistic implications
Clark, J. Stephen,Dossetter, Alexander G.,Wong, Yung-Sing,Townsend, Robert J.,Whittingham, William G.,Russell, C. Adam
, p. 3886 - 3898 (2007/10/03)
The intramolecular insertion of rhodium carbenoids into the α-C-H bonds of allylic ethers to give 3(2H)-furanones has been explored. Cyclopropanation is favored irrespective of the complex used for carbenoid generation or the substitution pattern of the allylic ether, unless a substituent is placed on the tether connecting the ether to the α-diazo ketone. Unusual acetal products resulting from an anomalous C-H insertion process are obtained in addition to the expected 3(2H)-furanones formed by conventional carbenoid C-H insertion. These acetals are the favored C-H insertion products in certain circumstances and particularly in cases where carbenoid generation is effected using an electron-deficient rhodium complex. Experiments with simple deuterium labeled substrates reveal that anomalous C-H insertion products arise by a mechanism that is distinct from that leading to the formation of conventional C-H insertion products. The formation of acetal products and the outcome of reactions performed using deuterium-labeled substrates suggest that a mechanism involving hydride migration to the rhodium center of the carbenoid is operative.
