Suzuki−Miyaura Cross-Coupling of 1,1-Dichloro-1-alkenes with 9-Alkyl-9-BBN

Abstract

We addressed an unexplored application of the Suzuki-Miyaura protocol to the cross-coupling of 1,1-dichloro-1-alkenes with 9-alkyl-9-BBN. The use of bisphosphine ligands with a large P-Pd-P bite angle allowed us to synthesize Z-chlorinated internal alkenes in good yields resulting from a selective monocoupling process, a recurrent challenge with 1,1-dichloro-1-alkenes. Moreover, these monochlorinated olefins could be further transformed providing stereospecifically trisubstituted olefins.

Aqueous Suzuki coupling reaction catalyzed by water-soluble diimine/Pd(II) systems

“…Lots of highly active supporting ligands have been developed for Suzuki coupling reaction, such as phosphine ligands [10,11], N-heterocyclic carbene ligands [12][13][14], palladacycle [15][16][17][18]. Recently, Suzuki reaction in aqueous phase including neat water and water/organic co-solvent has also received much more attention.…”

Various Entries to Vinyl Chloride Derivatives and their Applications in Total Synthesis of Natural Products

“…Palladium-Catalyzed Cross-Coupling of 1,1-Dichloro-1-alkenes with Alkyl-9-BBN 15 The use of alkyl-9-BBN nucleophilic partners in Pd 0 -catalyzed cross-coupling 16 is a particularly efficient way to create sp 3 -sp 2 carbon-carbon bonds; it is such a reliable strategy that it has been used very extensively in total synthesis. 17 The required alkene hydroboration step using 9-H-9-BBN can be included in a retrosynthetic plan with confidence, since the reaction is usually clean, regio-and chemoselective, and works under mild conditions.…”

2‐Substituted Benzo[b]furans from (E)‐1,2‐Dichlorovinyl Ethers and Organoboron Reagents: Scope and Mechanistic Investigations into the One‐Pot Suzuki Coupling/Direct Arylation

“…Alkyl groups could be installed via Negishi coupling [33] or using Suzuki coupling of an alkyl borane [34] but the onepot conversion to benzofurans 42 and 44 was incomplete even after days of reflux (Scheme 4). Subjecting the isolated intermediates 41 or 43 to these conditions did not improve the result.…”