Ni‐Catalyzed α‐Alkylation of Unactivated Amides and Esters with Alcohols by Hydrogen Auto‐Transfer Strategy. Issue 22 (5th November 2018)

• Record Type: Journal Article
• Authors: Midya, Siba P.; Rana, Jagannath; Pitchaimani, Jayaraman; Nandakumar, Avanashiappan; Madhu, Vedichi; Balaraman, Ekambaram
• Is Part Of: ChemSusChem. Volume 11:Issue 22(2018)
• Page Start: 3911
• Page End: 3916
• Publication Date: 2018-11-05
• Subjects: amides -- alkylation -- homogeneous catalysis -- hydrogen transfer -- nickel; Green chemistry -- Periodicals; Sustainable engineering -- Periodicals; Chemistry -- Periodicals; Chemical engineering -- Periodicals; 660
• DOI: 10.1002/cssc.201801443
• Languages: English
• ISSNs: 1864-5631

Abstract

Abstract: A transition‐metal‐catalyzed borrowing hydrogen/hydrogen auto‐transfer strategy allows the utilization of feedstock alcohols as an alkylating partner, which avoids the formation of stoichiometric salt waste and enables a direct and benign approach for the construction of C‐N and C−C bonds. In this study, a nickel‐catalyzed α‐alkylation of unactivated amides and ester ( tert ‐butyl acetate) is carried out by using primary alcohols under mild conditions. This C−C bond‐forming reaction is catalyzed by a new, molecularly defined nickel(II) NNN‐pincer complex (0.1–1 mol %) and proceeds through hydrogen auto‐transfer, thereby releasing water as the sole byproduct. In addition, N ‐alkylation of cyclic amides under Ni‐catalytic conditions is demonstrated. Abstract : A nickel(II) NNN‐pincer ‐catalyzed α‐alkylation of unactivated amides and ester ( tert ‐butyl acetate) is carried out by using primary alcohols under mild conditions proceeding by a borrowing hydrogen/hydrogen auto‐transfer mechanism. This C−C bond‐forming reaction releases water as the sole byproduct. N ‐Alkylation of cyclic amides under Ni‐catalytic conditions is also demonstrated.