7515-29-9Relevant academic research and scientific papers
Enantioconvergent alkylation of ketones with racemic secondary alcohols: Via hydrogen borrowing catalysis
Cheang, Daniella M. J.,Armstrong, Roly J.,Akhtar, Wasim M.,Donohoe, Timothy J.
supporting information, p. 3543 - 3546 (2020/04/03)
An enantioconvergent method for the alkylation of o-disubstituted aryl ketones with racemic secondary alcohols is described. This process is mediated by a commercially available iridium catalyst and proceeds via hydrogen borrowing catalysis. The highly enantioenriched β-substituted ketone products were readily cleaved to a wide range of functional groups via retro-Friedel-Crafts acylation.
Vicinal, Double C-H Functionalization of Alcohols via an Imidate Radical-Polar Crossover Cascade
Nagib, David A.,Prusinowski, Allen F.,Twumasi, Raymond K.,Wappes, Ethan A.
supporting information, (2020/03/16)
A double functionalization of vicinal sp3 C-H bonds has been developed, wherein a β amine and γiodide are incorporated onto an aliphatic alcohol in a single operation. This approach is enabled by an imidate radical chaperone, which selectively affords a transient β alkene that is amino-iodinated in situ. Overall, the radical-polar-crossover cascade entails the following key steps: (i) β C-H iodination via 1,5-hydrogen atom transfer (HAT), (ii) desaturation via I2 complexation, and (iii) vicinal amino-iodination of an in situ generated allyl imidate. The synthetic utility of this double C-H functionalization is illustrated by conversion of aliphatic alcohols to a diverse collection of α,β,γsubstituted products bearing heteroatoms on three adjacent carbons. The radical-polar crossover mechanism is supported by various experimental probes, including isotopic labeling, intermediate validation, and kinetic studies.
NEW ORGANOCOPPER REAGENTS PREPARED UTILIZING HIGHLY REACTIVE COPPER
Rieke, Reuben D.,Wehmeyer, Richard M.,Wu, Tse-Chong,Ebert, Greg W.
, p. 443 - 454 (2007/10/02)
Highly reactive copper solutions have been prepared by the lithium naphthalide reduction of copper(I) iodide/trialkylphosphine complexes.These activated copper solutions will react with organic halides under very mild conditions to form stable organocopper reagents.Significantly, the organocopper reagents can contain considerable functionalities such as ester, nitrile, chloride, epoxide, and ketone groups.These functionalized organocopper species undergo many reactions typical of other organocopper species.Intermolecular 1,4-additions, epoxide-opening reactions, and ketone formation with acid chlorides have been successfully achieved.In addition, this methodology has been applied to an intramolecular epoxide-cleavage reaction.The influence of the connecting chain length, substitution pattern, reaction solvent, and CuI/phosphine complex upon the regioselectivity of the intramolecular cyclization is described.
DIRECT FORMATION OF EPOXYALKYLCOPPER REAGENTS FROM ACTIVATED COPPER AND EPOXYALKYL BROMIDES AND THEIR INTRAMOLECULAR CYCLIZATIONS
Wu, Tse-Chong,Rieke, Reuben D.
, p. 6753 - 6756 (2007/10/02)
Epoxyalkylcopper compounds have readily been prepared by the direct oxidative addition of active copper to epoxyalkyl halides.The intramolecular cyclization of the epoxyalkylcopper reagents via an epoxide cleavage process is described.Significantly, many functional groups can be present in the bromoepoxides yielding highly functionalized carbocycles.The regioselectivity of this cyclizations is affected by the connecting chain length, substitution pattern, reaction solvent, and the CuI-phosphine complex used to generate the copper.
