Palladium(II)-Catalyzed Annulative Difunctionalization of Two Inert C(sp3)–H Bonds by a Bifunctional Reagent,ACS Catalysis

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Palladium(II)-Catalyzed Annulative Difunctionalization of Two Inert C(sp3)–H Bonds by a Bifunctional Reagent
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-05-22 , DOI: 10.1021/acscatal.3c01109
Arghadip Ghosh ₁ , Nicolas Grimblat _{2,

3} , Somratan Sau ₁ , Arijit Saha ₁ , Vincent Gandon _{2,

3} , Akhila K. Sahoo ₁

Affiliation

Illustrated herein is a Pd(II)-catalyzed direct difunctionalization of two C(sp³)–H bonds of aliphatic carboxylic acid derivatives by bifunctional reagents (BFRs) of the 2-iodobenzoic acid series. The methyl 2-pyridyl sulfoximine (MPyS) bidentate directing group (DG), 2-chloro-5-trifluoromethylpyridine ligand, AgOAc as a base, and NaBrO₃ as a co-oxidant help the concerted metalation deprotonation (CMD) of inert C(sp³)–H bonds, as well as the reductive elimination; density functional theory (DFT) studies shed light on these crucial steps. This process makes two bonds [C–C and C–O] at gem-α,α′-di-Me groups in a single operation, offering access to unusual benzo-fused peripheral-substituted caprolactones. The transformation tolerates labile functional groups and allows the construction of a wide range of caprolactones with structural diversity. Mechanistic studies reveal the participation of monomeric Pd species in the catalytic cycle. The synthetic versatility of the complex molecular entities is also presented.

中文翻译：

双功能试剂钯 (II) 催化两个惰性 C(sp3)–H 键的环形双功能化

本文举例说明了通过 2-碘苯甲酸系列的双功能试剂 (BFR)，Pd(II) 催化的脂肪族羧酸衍生物的两个 C(sp ^{3 )–H 键的直接双功能化。}甲基 2-吡啶基亚砜亚胺 (MPyS) 双齿导向基团 (DG)、2-氯-5-三氟甲基吡啶配体、AgOAc 作为碱和 NaBrO 3 作为助氧化剂有助于惰性_C ( sp ³ )–H键，以及还原消除；密度泛函理论 (DFT) 研究阐明了这些关键步骤。此过程在gem处形成两个键 [C–C 和 C–O]-α,α'-di-Me 基团在一次操作中，提供了获得不寻常的苯并稠合外周取代己内酯的途径。这种转变容忍不稳定的官能团，并允许构建范围广泛的具有结构多样性的己内酯。机理研究揭示了单体 Pd 物种参与催化循环。还介绍了复杂分子实体的合成多功能性。

更新日期：2023-05-22

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