Stereoselective C−B and C−H Bonds Functionalization of PolyBorylated Alkenes DOI Creative Commons

Narendra Kumar Vaishanv,

Nadim Eghbarieh, Rahul A. Jagtap

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(45)

Published: July 9, 2024

Abstract Alkenes are fundamental functional groups which feature in various materials and bioactive molecules; however, efficient divergent strategies for their stereodefined synthesis difficult. In this regard, numerous synthetic methodologies have been developed to construct carbon–carbon bonds with regio‐ stereoselectivity, enabling the predictable of alkenes. fact, an appealing alternative approach accessing challenging alkene molecular frameworks could involve sequential selective activation cross‐coupling strong instead conventional C−C bond formation. study, we introduce a series programmed site‐ stereoselective that capitalizes on versatile reactivity readily accessible polymetalloid alkenes (i.e. polyborylated alkenes), through tandem reaction, is catalyzed by organometallic Rh‐complex produce complex scaffolds. By merging C−B remote C−H functionalization, achieve situ generation polyfunctional C(sp 2 )‐nucleophilic intermediates. These species can be further modified coupling reactions C‐based electrophiles, formation )−C(sp 3 ) even more architectures using available starting polyborylated‐alkenes. Mechanistic computational studies provide insight into origins stereoselectivities via 1,4‐Rh migration process.

Language: Английский

Pd‐Catalyzed Cross‐Coupling of Alkylbisboronic Esters DOI Creative Commons
Peter J. H. Scott, Christopher W. Baird,

Elizabeth A. Kraichely

et al.

ChemistryOpen, Journal Year: 2025, Volume and Issue: unknown

Published: April 10, 2025

A Pd-catalyzed cross-coupling between alkylbisboronic esters and aryl bromides is described. variety of are found to be competent substrates in the reaction. Different alkyl chain lengths examined, a two-carbon linker optimal length. Several competition experiments performed better understand mechanism

Language: Английский

Citations

0
Orthogonal sp3‐Ge/B Bimetallic Modules: Enantioselective Construction and Enantiospecific Cross‐Coupling DOI
Mengyu Xu, Weitao Jiang,

Ming‐Zhi Xia

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 12, 2024

Abstract In this study, a series of enantioenriched sp 3 ‐Ge/B bimetallic modules were successfully synthesized via an enantioselective copper‐catalyzed hydroboration carbagermatrane ( Ge )‐containing alkenes. Orthogonal cross‐coupling selectivity under different Pd‐catalyzed conditions was achieved in enantiospecific manner. Notably, the chiral secondary exhibited remarkable transmetallation ability prior to primary or Bpin. The effectiveness Ge/B strategy further demonstrated through development new functional small molecules with Aggregation‐Induced Emission (AIE) and Circularly Polarized Luminescence (CPL) performance. This represents first successful example synthesis alkylgermanium reagents that permit reactions.

Language: Английский

Citations

3
Recent Advances in Catalytic Asymmetric Synthesis of Chiral 1,2-Bis(boronic) Esters DOI Open Access
Chong‐Lei Ji, De‐Wei Gao

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(5), P. 1385 - 1385

Published: Jan. 1, 2024

Chiral 1,2-bis(boronic) esters are essential building blocks in the field of synthetic chemistry, and their catalytic asymmetric synthesis has attracted significant interest chemists.Recently, diboration olefins, using transition metals chiral diols, emerged as straightforward atom-economical methods for producing highly valuable esters.Asymmetric hydrogenation vinyl bis(boronic) can be a complementary approach to synthesizing these products.Additionally, borofunctionalization alkenes or alkynes represents another effective strategy constructing scaffolds.A recent innovation involves migratory coupling reactions with gem-diborylalkanes, offering new avenues esters.The latest developements challenges moleculeshis summarized, potential future research directions this prospected.

Language: Английский

Citations

3
Catalytic asymmetric synthesis of meta benzene isosteres DOI
Mingkai Zhang, Matthew Chapman, Bhagyesh R. Sarode

et al.

Nature, Journal Year: 2024, Volume and Issue: 633(8028), P. 90 - 95

Published: Aug. 21, 2024

Language: Английский

Citations

3
Catalytic Selective Functionalization of Poly(organoborons)† DOI
Jiahui Zhao, Ang Chen,

Xi‐Zhang Zou

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 28, 2024

Comprehensive Summary Organoborons are commonly used building blocks for rapidly increasing molecular complexity. Although significant progress has been made in the selective functionalization of mono‐organoborons, site‐selective poly(organoborons) attracted substantial interest organic synthesis, pharmaceuticals, and agrochemicals due to presence multiple potential reaction sites. This review discusses various activation modes target C–B bond, with diverse transformations being achieved both a efficient manner. Recent advances catalytic 1, n ‐diboronates through ionic radical pathways highlighted. Furthermore, we summarize existing challenges future research directions this field. Key Scientists In 1993, Suzuki, Miyaura coworkers developed pioneering example arylation towards cis‐1,2‐bis(boryl) alkenes, marking inception The Morken group contributions asymmetric diboration alkenes realized elegant these compounds since 2004. 2016, Fernández colleagues internal bond tri(boronates). Since 2019, Aggarwal Giese‐type addition at more substituted 1,2‐bis(boronic) esters photoredox catalysis. controllable regiodivergent alkynylation 1,3‐bis(boronic) was by Gao 2023. Recently, Qin conducted on programmable late‐stage bridge‐substituted bicyclo[1.1.1]pentane (BCP) bis‐boronates. 2013, stereoselective have several groups, including those led Chen. summarizes latest most developments field 1993.

Language: Английский

Citations

3
Divergent Synthesis of 1,2,3,4‐Tetrasubstituted Cyclobutenes from a Common Scaffold: Enantioselective Desymmetrization by Dual‐Catalyzed Photoredox Cross‐Coupling DOI Creative Commons
Dawson J. Konowalchuk, Dennis G. Hall

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Oct. 19, 2023

Four-membered carbocycles are important structural motifs found in several natural products and drugs. Amongst those, cyclobutenes attractive intermediates because the residual olefin can be manipulated selectively into various saturated unsaturated analogs. Few methods exist to access chiral tri- tetra-C-substituted they generally limited terms of diversification. Herein, a divergent synthetic strategy was developed where single optically enriched scaffold is diversified variety derivatives with different substitution patterns. To this end, enantioselective desymmetrization prochiral 1,2-dibromocyclobutene imides enabled by dual Ir/Ni-catalyzed photoredox C(sp2 )-C(sp3 ) cross-coupling an alkyltrifluoroborate salt install convertible carbon fragment good yields >90 % enantiomeric excess. Exceptional mono-coupling selectivity observed resulting bromocyclobutene serves as common that transformed manner valuable 1,2,3,4-tetra-C-substituted cyclobutane while maintaining optical purity.

Language: Английский

Citations

8
Visible Light Catalyzed Reductive Cross‐Coupling of α‐CF3‐alkyl Bromide and Alkynyl Bromide† DOI

Yiqiang Tian,

Yi Li, Chun Zhang

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(20), P. 2479 - 2484

Published: June 21, 2024

Comprehensive Summary Traditional reduction coupling reactions of two bromides typically rely on transition metal catalysis. Here, we introduce the development a visible‐light catalytic direct reaction between α ‐CF 3 ‐alkyl and alkynyl to access valuable organic frameworks. Our research confirms excellent compatibility this with various functional groups, which could be used modify substrate biologically active molecular fragments. Mechanistic investigations, including control experiments, fluorescence quenching studies, light‐switching have provided insights into mechanism. This study paves way for application catalysis in diverse synthetic transformations, offering sustainable efficient approach synthesis.

Language: Английский

Citations

2
Controllable Regiodivergent Alkynylation of 1,3‐Bis(Boronic) Esters Activated by Distinct Organometallic Reagents DOI Open Access
Ang Chen, Qiao Yang, De‐Wei Gao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(48)

Published: Oct. 18, 2023

1,3-Bis(boronic) esters can be readily synthesized from alkylBpin precursors. Selective transformations of these compounds hold the potential for late-stage functionalization remaining C-B bond, leading to a diverse array molecules. Currently, there are no strategies available address reactivity and, more importantly, controllable regiodivergent 1,3-bis(boronic) esters. In this study, we have achieved alkynylation The regioselectivity has been clarified based on unique chelation patterns observed with different organometallic reagents. Remarkably, methodology effectively addresses low and bridges gap in radical chemistry, which typically yields only classical products formed via stable intermediates. Furthermore, through approach serve as potent building blocks creating molecular diversity.

Language: Английский

Citations

4
Desymmetrization of Cyclohexadienones Containing a Quaternary γ-Carbon Atom by Conjugate Addition of Boron Nucleophiles DOI
Zhiyuan Zhao, Ming Cui, A. Poletti

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(1), P. 176 - 182

Published: Dec. 12, 2023

A highly enantio- and diastereoselective copper-catalyzed conjugate monoborylation of γ,γ-disubstituted cyclohexadienone derivatives is reported. Two contiguous stereocenters are generated in this group-selective reaction, one at the formed boron-bearing carbon atom a neopentylic position quaternary atom. subsequent 1,4-addition boron nucleophile to remaining α,β-unsaturated acceptor allows for construction another stereocenter other position, thereby leading three adjacent stereogenic atoms congested environment. The diastereoselectivity that second borylation can be controlled by different chiral ligands selectively afford either syn- or anti-1,3-diborylated product.

Language: Английский

Citations

4
Tandem Diboration–Protoboration of Terminal Alkynes: A Practical Route to α-Substituted Alkenyl Boronates DOI
James P. Morken, Ziyin Kong, Jimin Park

et al.

Synlett, Journal Year: 2024, Volume and Issue: unknown

Published: June 5, 2024

Abstract A practical method is introduced for the catalytic conversion of terminal alkynes into α-substituted vinyl boronic esters. The process employs amounts nanoparticle-supported gold catalysts and copper to effect overall transformation.

Language: Английский

Citations

1