Palladium-Catalyzed Desulfitative Oxidative Coupling between Arenesulfinic Acid Salts and Allylic Alcohols: A Strategy for the Selective Construction of β-Aryl Ketones and Aldehydes

Abstract

An efficient palladium-catalyzed desulfitative oxidative coupling of sodium arylsulfinites for highly region-selective Heck-type reaction of allylic alcohols has been developed. The compatibility of the functionalities of -I, -Br, and -F would explore further postfunctionalization of the C-X bonds. This method provides a new and straightforward protocol for the synthesis of β-aryl ketones and aldehydes. The deuterium labeling experiments indicated that this transformation may proceed via a [1, 2-H] shift process.

Palladium Catalysis for Aerobic Oxidation Systems Using Robust Metal–Organic Framework

“…Based on above results and previous reports, we propose a plausible mechanism of the Pd‐catalyzed oxidative coupling reaction within UiO‐67‐phen‐Pd/Cu(1:2) (Scheme ). The aromatic sulfinic sodium is firstly coordinated to Pd II in the MOF with the extrusion of SO 2 .…”

“…As a proof‐of‐concept, the Pd‐catalyzed desulfitative oxidative coupling between arenesulfinic acid salts and an allylic alcohol was selected as a model reaction to verify the MOF‐based catalytic system because this reaction possesses the representative oxidation and catalysis problems of Pd‐catalyzed AOSs. For example, the homogeneous system needs a high loading of Pd(TFA) 2 (10 mol %) as the catalyst, phenanthroline (phen; 20 mol %) as the ligand, and a stoichiometric amount of Cu(TFA) 2 as the ETM to achieve high reactivity.…”

Palladium Catalysis for Aerobic Oxidation Systems Using Robust Metal–Organic Framework

“…Based on above results and previous reports, [7] we propose a plausible mechanism of the Pd-catalyzed oxidative coupling reaction within UiO-67-phen-Pd/Cu(1:2) (Scheme 3). The aromatic sulfinic sodium is firstly coordinated to Pd II in the MOF with the extrusion of SO 2 .…”

“…As a proof-of-concept, the Pd-catalyzed desulfitative oxidative coupling [7] between arenesulfinic acid salts and an allylic alcohol was selected as a model reaction to verify the MOF-based catalytic system because this reaction possesses the representative oxidation and catalysis problems of Pdcatalyzed AOSs. For example, the homogeneous system needs a high loading of Pd(TFA) 2 (10 mol %) as the catalyst, phenanthroline (phen; 20 mol %) as the ligand, and a stoichiometric amount of Cu(TFA) 2 as the ETM to achieve high reactivity.…”

Copper-catalysed regioselective sulfenylation of indoles with sodium sulfinates

“…Because they are inexpensive, stable and easy to handle, they have been widely used as sulfonylating agents [ 29 – 32 ] and arylating agents [ 33 ], especially in recent years. In 2014, Deng and co-workers first reported the use of sodium sulfinates as sulfenylating agents for the synthesis of 3-sulfenylindole with dimethyl sulfoxide (DMSO) as the oxidant and diethyl phosphite as the reductant ( scheme 1 a ) [ 32 , 34 – 37 ]. Thereafter, Kuhakarn's group carried out similar work with a I 2 /PPh 3 reaction system ( scheme 1 b ) [ 38 ].…”