75424-63-4Relevant articles and documents
Nickel-Catalyzed Decarboxylative Coupling of Redox-Active Esters with Aliphatic Aldehydes
Xiao, Jichao,Li, Zhenning,Montgomery, John
, p. 21234 - 21240 (2021/12/27)
The addition of alkyl fragments to aliphatic aldehydes is a highly desirable transformation for fragment couplings, yet existing methods come with operational challenges related to the basicity and instability of the nucleophilic reagents commonly employed. We report herein that nickel catalysis using a readily available bioxazoline (BiOx) ligand can catalyze the reductive coupling of redox-active esters with aliphatic aldehydes using zinc metal as the reducing agent to deliver silyl-protected secondary alcohols. This protocol is operationally simple, proceeds under mild conditions, and tolerates a variety of functional groups. Initial mechanistic studies suggest a radical chain pathway. Additionally, alkyl tosylates and epoxides are suitable alkyl precursors to this transformation providing a versatile suite of catalytic reactions for the functionalization of aliphatic aldehydes.
Generation of alkyl radicals from alkylsilyl peroxides and their applications to C-N or C-O bond formations
Sakurai, Shunya,Kato, Terumasa,Sakamoto, Ryu,Maruoka, Keiji
, p. 172 - 179 (2018/12/11)
This article describes a novel method for the generation of alkyl radicals from alkylsilyl peroxides and their applications to the Cu-catalyzed mono-N-alkylation of amides or arylamines, and to the O-alkylation of carboxylic acids. The use of alkylsilyl peroxides as alkyl radical sources includes the following synthetic advantages: i) various alkylsilyl peroxides can be readily synthesized from the corresponding alcohols and be stored at bench, and ii) a variety of alkyl radicals can be generated efficiently under mild conditions.
Alkylsilyl Peroxides as Alkylating Agents in the Copper-Catalyzed Selective Mono-N-Alkylation of Primary Amides and Arylamines
Sakamoto, Ryu,Sakurai, Shunya,Maruoka, Keiji
supporting information, p. 9030 - 9033 (2017/07/11)
The copper-catalyzed selective mono-N-alkylation of primary amides or arylamines using alkylsilyl peroxides as alkylating agents is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the alkylsilyl peroxides, as well as to the primary amides and arylamines. Mechanistic studies suggest that the present reaction should proceed through a free-radical process that includes alkyl radicals generated from the alkylsilyl peroxides.