摘要：AshirwadDivedi, Saumya Verma, Dinesh Chandra, Shivam Bhargav, Ved Prakash Verma, andJawahar L. Jat*

转自：康龙化成

Metal-Free Direct Synthesis ofSecondary Amides and Nitriles Using O-(2-Pyrimidinyl)-N-Boc Hydroxylamine

AshirwadDivedi, Saumya Verma, Dinesh Chandra, Shivam Bhargav, Ved Prakash Verma, andJawahar L. Jat*

Department of Chemistry, School ofPhysical and Decision Science Babasaheb Bhimrao Ambedkar University (A CentralUniversity), India

—Eur.J. Org. Chem. 2024, e202401229

Recommended by Bing Han_MC3

KEY WORDS:Beckmannrearrangement (反应类型),O-(2-pyrimidinyl)-N-Boc hydroxylamine, ketones, aldehydes (反应物), amides, nitriles (产物); C(sp2)-N,C(sp3)-N (成键类型)

ABSTRACT: Anovel hydroxylamine-derived aminating agent, O-(2-pyrimidinyl)-N-Bochydroxylamine (PymONHBoc), has been designed and synthesized, fromreadily available 2-chloropyrimidine. This reagent demonstrates superior shelfstability and ease of handling compared to other hydroxylamine derivedreagents. Here, we present a metal-free method for the direct conversion ofketones and aldehydes into sec-amides and nitriles using PymONHBoc asthe aminating agent. This method efficiently converts a wide range of aliphaticand aromatic carbonyl compounds into the corresponding amides and nitriles withgood to excellent yields under ambient conditions. The use of PymONHBoc isadvantageous, as it facilitates the in situ generation of the activated oximeintermediate, concomitantly producing a non-interfering byproduct.

Background

Optimizationof reaction conditions

Selectedsubstrate scope of amidation of ketones

Scopeof nitriles synthesis

Prof.Jawahar L. Jat and his co-workersreported asynthetic applications of the novel O-(2-pyrimidinyl)-N-Bochydroxylamine reagent forthe Beckmannrearrangement under mildand metal-free condition at ambient temperature. The TGA study indicates that thisnewly developed reagent is more stable compared to other similar reagents. Thismethod is operationallysimple, demonstrates broad scope, and exhibits good functional group tolerance.Additionally, the reaction can be performed on a gramscale. Weanticipate that this reagent and method will find valuable applications insynthetic chemistry.

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