Cooperative Pd/Cu Catalysis for Alkene Arylboration: Opportunities for Divergent Reactivity

Abstract

A preeminent challenge in alkene difunctionalization is the control of regio-, diastereo-, and enantioselectivity. In this Perspective, a Pd/Cu-cooperative catalytic system for alkene arylboration is highlighted that allows for the controlled introduction of substituents. In particular, examples that allowed for divergent reactivity from a single substrate based on the tuning of catalysts and reaction conditions are emphasized.

Recent Applications on Dual-Catalysis for C–C and C–X Cross-Coupling Reactions

“…In this protocol, the authors screened various alkene substrates, such alkenylarenes 100 (Scheme 24, left side), 1,3-dienes 103 (Scheme 24, right side), and 1-substituted alkenylarenes 106 (Scheme 25, left side) resulting in good yields with excellent diastereoselectivities. 89 The authors proposed a reaction mechanism based on the literature and their previous experience with reactions of 1,1-and 1,2-disubstituted derivatives; the plausible mechanism has been presented in Scheme 25 (right side).…”

Copper catalyzed borocarbonylation of benzylidenecyclopropanes through selective proximal C–C bond cleavage: synthesis of γ-boryl-γ,δ-unsaturated carbonyl compounds

“…Recently, impressive progress has been made in copper catalyzed borylative difunctionalization of π-systems, which provides a promising strategy for rapid generation of molecular complexity to install a boron and unique groups across π-systems. 5 These processes are particularly valuable since the resulting C–B bond could be transformed into various functional groups via C–C and C–heteroatom bond-forming reactions through stereospecific transformations. 6 The key step in these reactions is the addition of Cu–Bpin species to C–C π-bonds to give the corresponding β-borylalkylcopper intermediates, which could be captured by various electrophiles to give the difunctionalized products ( Scheme 1a ).…”

A unified approach to access β-branched organoboron through coupling of boron-stabilized organozinc with alkyl halides

“…In addition, the Brown group developed an elegant strategy for the synthesis of β-quaternary organoboron compounds through transition-metal catalyzed 1,2-alkenylboration, borylacylation and arylboration of 1,1-disubstituted alkenes. [41][42][43][44][45][46][47] It is worth mentioning that, boron-functionalization of monosubstituted alkenes would give the β-tertiary boronic esters. [48][49][50][51][52][53][54][55][56][57][58][59][60][61][62][63][64] Moreover, Yu, 65 Sawamura, 66 Shi 67 and Hartwig 68 had independently reported the transitionmetal (Pd or Ir)-catalyzed directed borylation of terminal C(sp 3 )-H bond to prepare the β-branched organoboron compounds.…”