Pd(II)-Catalyzed Denitrogenative and Desulfinative Addition of Arylsulfonyl Hydrazides with Nitriles

Abstract

A Pd(II)-catalyzed denitrogenative and desulfinative addition of arylsulfonyl hydrazides with nitriles has been successfully achieved under mild conditions. This transformation is a new method for the addition reaction to nitriles with arylsulfonyl hydrazides as arylating agent, thus providing an alternative synthesis of aryl ketones. The reported addition reaction is tolerant to many common functional groups, and works well in the presence of electron-donating and electron-withdrawing substituents. Notably, the reported denitrogenative and desulfinative addition was also appropriate for alkyl nitriles, making this newly developed transformation attractive.

Sulfonyl Hydrazides in Organic Synthesis: A Review of Recent Studies

“…On the other hand, the nucleophilic addition of organometallic reagents to nitriles is a well‐known reaction for ketone preparation. The Cheng group elaborated a Pd‐catalyzed denitrogenative and desulfinative addition from sulfonyl hydrazides (Eq. 61‐3).…”

“…61‐3). In these methods, water functioned as the co‐solvent or O‐source for the hydrolysis(Scheme ).…”

Efficient Tandem Addition/Cyclization for Access to 2,4-Diarylquinazolines via Catalytic Carbopalladation of Nitriles

“…Since Larock’s pioneering work on the development of the catalytic carbopalladation of nitriles [5,6,7], remarkable progress in the transition metal catalyzed addition of organoboron reagents to nitriles has been documented during the past several decades by several other groups [8,9,10,11] and our group [12,13,14]. In recent years, the scope of this chemistry has been significantly expanded to other coupling partners, including sodium aryl sulfinates or arylsulfinic acids [15,16,17,18], aryl halides [19,20], benzoic acids [21], arylhydrazines [22], and arylsulfonyl hydrazides [23]. However, this transformation of nitriles exclusively provides aryl ketone products (Scheme 1a).…”

Desulfinative palladium‐catalyzed cross‐coupling of arylsulfonyl hydrazides with aryl bromides under air

“…Zhou's groups have employed arylsulfonyl hydrazides as aryl sources in Hiyama coupling reactions by desulfitation . Pd‐catalyzed desulfinative cross‐coupling of arylsulfonyl hydrazides has been well studied, such as Heck coupling, Sonogashira coupling, homocoupling, iodination and addition . However, the new‐type Pd‐catalyzed desulfitative cross‐coupling of arylsulfonyl hydrazides with aryl bromides was still obscured.…”

“…[56] Pd-catalyzed desulfinative crosscoupling of arylsulfonyl hydrazides has been well studied, such as Heck coupling, [47] Sonogashira coupling, [50] homocoupling, [57] iodination [49] and addition. [58] However, the new-type Pd-catalyzed desulfitative crosscoupling of arylsulfonyl hydrazides with aryl bromides was still obscured. Herein, we would like to describe a simple and efficient palladium-catalyzed cross-coupling of arylsulfonyl hydrazides and aryl bromides for the selective synthesis of unsymmetrical biaryls.…”