Suzuki Coupling Of Arylboronic Acids Research Articles

Construction of α‐(Hetero)aryl Ethenesulfonyl Fluorides for SuFEx Click Chemistry

The construction of α‐(hetero)aryl ethenesulfonyl fluorides was achieved via a Pd‐catalyzed Suzuki coupling of arylboronic acids with 1‐bromoethene‐1‐sulfonyl fluoride (1‐Br‐ESF). The novel α‐aryl ethenesulfonyl fluorides were found to be another selectively addressable bis‐electrophile for wide diversification through SuFEx click chemistry, or Michael addition with excellent chemical discrimination.

Synthesis of bromodifluoromethyl(arylsulfonyl) compounds and microwave-assisted nickel catalyzed cross coupling with arylboronic acids

A nickel catalyzed Suzuki coupling of arylboronic acids and novel bromodifluoromethyl(arylsulfonyl) compounds is described, providing an example of direct Csp2-CF2SO2Ar bond formation. High-throughput experimentation (HTE) was utilized for identifying the catalyst and reaction conditions.

N-heterocyclic carbene-assisted, bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates.

Efficient bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates have been effected with an assistance of N-heterocyclic carbene (NHC) generated in situ from N,N'-dialkylimidazoliums, e.g., N-butyl-N'-methylimidazolium bromide ([Bmim]Br), in toluene using K3PO4·3H2O as base. In contrast to bis(NHC)nickel-catalyzed conventional Suzuki coupling of arylboronic acids, mono(NHC)bis(phosphine)nickel species generated in situ from Ni(PPh3)2Cl2/[Bmim]Br displayed high catalytic activities in the cross-couplings of diarylborinic acids. The structural influences from diarylborinic acids were found to be rather small, while electronic factors from aryl chlorides, tosylates, and sulfamates affected the couplings remarkably. The couplings of electronically activated aryl chlorides, tosylates, and sulfamates could be efficiently effected with 1.5 mol % NiCl2(PPh3)2/[Bmim]Br as catalyst precursor to give the biaryl products in excellent yields, while 3-5 mol % loadings had to be used for the couplings of non- and deactivated ones. A small ortho-substitutent on the aromatic ring of aryl chlorides, tosylates, and sulfamates was tolerable. Applicability of the nickel-catalyzed cross-couplings in practical synthesis of fine chemicals has been demonstrated in process development for a third-generation topical retinoid, Adapalene.

Ligand-Free Suzuki Coupling of Arylboronic Acids with Methyl (E)-4-Bromobut-2-enoate: Synthesis of Unconventional Cores of HIV-1 Protease Inhibitors

An effective ligand-free Suzuki coupling protocol to unite methyl (E)-4-bromobut-2-enoate with several arylboronic acids has been accomplished. Thus, a number of variously functionalized methyl 4-arylcrotonates have been achieved in high to excellent yields under mild conditions. This method enables the preparation of diverse aryl-substituted cores of HIV-1 protease inhibitors.

A New Route to Biaryl Ketones via Carbonylative Suzuki Coupling Catalyzed by MCM‐41‐supported Bidentate Phosphine Palladium(0) Complex

AbstractA variety of biaryl ketones can be conveniently synthesized in good to high yields via the first heterogeneous carbonylative Suzuki coupling of arylboronic acids with aryl iodides under atmospheric pressure of carbon monoxide in the presence of a catalytic amount of MCM‐41‐supported bidentate phosphine palladium(0) complex [MCM‐41‐2P‐Pd(0)]. This polymeric palladium catalyst can be reused at least 10 times without any decrease in activity.

Synthesis of biphenyl-based phosphines by Suzuki coupling

A series of phosphine oxides has been synthesised by the palladium-catalysed Suzuki coupling of arylboronic acids with OPPh 2( o-C 6H 4Br). On reduction with trichlorosilane, functionalised, biphenyl-based phosphine ligands were obtained in good yields. Our preliminary results indicate these ligands to be effective for palladium-catalysed C–C coupling reactions including the formation of their own oxides.