Catalyst Development in the Dehydrogenative Borylation of Alkenes for the Synthesis Vinylboronate Esters

Abstract

Catalytic dehydrogenative borylation of alkenes provides an efficient and straightforward method for the preparation of synthetically useful vinylboronate esters. Here, we present a summary of developments and recent advances in this area, classified according to the various reactants and catalyst systems.1 Introduction2 Catalytic Dehydrogenative Borylation of Alkenes by Using Boranes3 Catalytic Dehydrogenative Borylation of Alkenes by Using Diboranes4 Zirconium-Catalyzed H 2 –Acceptorless Dehydrogenative Borylation of Alkenes with Boranes5 Conclusion and Outlook

Cyclododecene isomeric separation by (supported) rhodium(i)-catalysed selective dehydrogenative borylation reaction

“…1B). 5 Thus this reaction is very sensitive to the CC double bond configuration, so it may differentiate the cis / trans alkene diastereoisomers during reaction. Among the different catalysts employed for this reaction, which include the metals Ru, 6 Rh, 6 b ,7 Co, 8 Pd 9 and Pt, 10 and recently non-metal catalysts as well, 11 only Rh( i ) seems to have the capacity to perform alkene functionalization without associated diborylation and hydrogenation reactions, without losing any starting alkene.…”

“…1B). 5 Thus this reaction is very sensitive to the CvC double bond configuration, so it may differentiate the cis/trans alkene diastereoisomers during reaction. Among the different catalysts employed for this reaction, which include the metals Ru, 6 Rh, 6b,7 Co, 8 Pd 9 and Pt, 10 and recently Instituto de Tecnología Química (UPV-CSIC), Universidad Politècnica de València-Consejo Superior de Investigaciones Científicas, Avda.…”

Facile Synthesis of Vinyl Boronate Esters via Dehydrogenative Borylation of Alkenes Enabled by a Co-MOF Catalyst: An Additive-Free Approach

“…Among organoboron derivatives, vinyl boronate esters (VBEs) are important building blocks in organic synthesis . Selective direct dehydrogenative borylation of alkenes is an attractive tool to synthesize these derivatives in comparison to alkyne hydroboration, C-X borylation of alkenyl halides, boryl-Heck reaction of terminal alkenes, olefin cross metathesis of VBEs, or by traditional transmetalation approach .…”

Cobalt-Catalyzed Selective Hydroboration of 1,3-Enynes with HBpin toward 1,3-Dienylboronate Esters

“…Among them, vinylboronate esters are a representative and important class of organoboron reagents featuring low cost, low toxicity, and ease of storage and handling relative to most vinyl metal reagents, and they are employed in versatile synthetic transformations, such as Suzuki–Miyaura coupling, Chan–Lam coupling, Mannich reaction, Heck reaction, and Michael addition . Given their proven versatility, vinylboronates have become an attractive and valuable synthetic target, and many efficient catalytic methods have been well-developed . In contrast, 1,3-dienylboronates, the homologues of vinylboronates, equally with diverse synthetic transformations, have been much less studied in terms of their preparation, especially by efficient catalytic reactions …”