Copper‐Catalyzed Reduction of Alkyl Triflates and Iodides: An Efficient Method for the Deoxygenation of Primary and Secondary Alcohols

Abstract

We describe an effective method for catalytic reduction of 1° alkyl sulfonates, and 1° and 2° iodides in the presence of a wide range of functional groups. This Cu-catalyzed reaction provides a means for the effective deoxygenation of alcohols, as demonstrated by the highly selective reduction of 1° alcohols using a triflation/reduction sequence. A preliminary study of the reaction mechanism suggests that the reduction does not involve free-radical intermediates.

Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2 – The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates

“…In a similar vein, the Cu-catalyzed reduction of alkyl triflates to the corresponding alkane, has also been made available [126]. Applications in total synthesis of this reaction have been described by Faghihi and coworkers [127].…”

Tetramethyldisiloxane: A Practical Organosilane Reducing Agent

“…(Eq.142). 119 This is related to the pre-catalyst used by Yun for 1,2 /1,4 reductions. 107 Tosylates and nosylates were less noticeably reactive than the triflates.…”

Cu‐Catalyzed Hydroxymethylation of Unactivated Alkyl Iodides with CO To Provide One‐Carbon‐Extended Alcohols

“…We began our study with 1-iodo-3-phenylpropane (1a)as amodel substrate under 3atm of CO pressure.After screening all the various reaction parameters systematically, a Me IPrCuCl catalyst with the addition of 3.0 equiv of diethoxymethylsilane and 2.0 equiv of LiOMe was found to be critical to achieve good yield of the desired alcohol product ( Table 1, entry 1; see the Supporting Information for more details). Conducting the reaction at 60 8 8Ca nd at 3atm of CO pressure also were found to be required (entries [14][15]. Although other NHC ligands such as IPr, SIPr, Cl IPr, and IMes can be used in this transformation, they only provided moderate yields (entries 3-6).…”

“…[12] In these reactions,insitu generated alkyl radicals are carbonylated and coupled with organocopper nucleophiles to generate ketones.W eh ypothesized that under reductive conditions,c opper hydride nucleophiles could instead provide aldehydes,w hich would be expected to undergo further reduction under CuH catalysis to provide hydroxymethylated products through at andem carbonylation/reduction sequence (Scheme 1d). [14] Here,w er eport conditions that provide hydroxymethylation products from alkyl iodides with high selectivity. [14] Here,w er eport conditions that provide hydroxymethylation products from alkyl iodides with high selectivity.…”