摘要：Department of Chemistry and ChemicalBiology, Harvard University, Cambridge, Massachusetts 02138, United States

转自：康龙化成

Rapid and General Amination of ArylBoronic Acids and Esters Using O-(Diphenylphosphinyl)hydroxylamine(DPPH)

Matthew G. Kung, Polpum Onnuch andRichard Y. Liu*

Department of Chemistry and ChemicalBiology, Harvard University, Cambridge, Massachusetts 02138, United States

—Org.Lett. 2024, doi:10.1021/acs.orglett.4c03625

Recommended by Depei Meng_MC4

KEYWORDS: Amination(反应类型),C(sp2)–N (成键类型), aryl boronic acids (原料),aryl boronic esters (原料),anilines (产物), (DPPH) (试剂)

ABSTRACT: O-(Diphenylphosphinyl)hydroxylamine(DPPH) is a general reagent for the conversion of (hetero)aryl boronic acidsand esters to primary anilines. The transformation proceeds rapidly at rt andexhibits a broad substrate scope and exceptional functional-group tolerance. Interms of rate, the reaction is relatively insensitive to the electronicproperties of the substrate, in contrast to similar reactions usingelectrophilic amination reagents such as hydroxylamine-O-sulfonic acid.Consequently, this protocol is particularly useful for accessingelectron-deficient (hetero)aryl anilines, which had been challenging to prepareusing prior methods.

PrimaryAniline Synthesis. (A)Transition-metal-catalyzed cross coupling with ammonia methods. (B) Primaryamination of (hetero)aryl boronicacids using ambiphilic hydroxylamine-derived reagents.

Evaluation of Reaction Parameters

Selected Scope

ReactionMechanism and Transition State Structure (TS1) as Modeled by DFT

Inconclusion, Matthew G. Kung etal. reportthat O-(diphenylphosphinyl)-hydroxylamine(DPPH) ishighly effective for the conversion of aryl boronic acids and esters to anilines undermild conditions. The broad applicability of this reagent may be attributed toan operative mechanism whose rate is minimally influenced by the electronicproperties of the substrate.

总地来说，Matthew G. Kung等报道了O-(二苯基氧膦基)-羟胺(DPPH)在温和条件下有效将芳基硼酸和硼酸酯转化为苯胺的方法。另外，该转化的速率受底物电子特性的影响小，这可能是该试剂适用性好的原因。

来源：新浪财经