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

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 International Edition, Journal Year: 2024, Volume and Issue: 63(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

Citations

1
PolyBorylated Alkenes as Energy‐Transfer Reactive Groups: Access to Multi‐Borylated Cyclobutanes Combined with Hydrogen Atom Transfer Event DOI Creative Commons
Nicole Hanania, Nadim Eghbarieh, Ahmad Masarwa

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(25)

Published: April 11, 2024

Abstract While polyborylated alkenes are being recognized for their elevated status as highly valuable reagents in modern organic synthesis, allowing efficient access to a diverse array of transformations, including the formation C−C and C‐heteroatom bonds, potential energy‐transfer reactive groups has remained unexplored. Yet, this holds key generating elusive biradical species, which can be captured by olefins, thereby leading construction new highly‐borylated scaffolds. Herein, we report designed strategy photosensitized [2+2]‐cycloadditions poly‐borylated with various olefins enabling regioselective synthesis cyclobutane motifs, 1,1‐di‐, 1,1,2‐tri‐, 1,1,2,2‐tetra‐borylated cyclobutanes. In fact, these compounds belong family that presently lacks synthetic pathways. Interestingly, when α‐methylstyrene was used, reaction involves an interesting 1,5‐hydrogen atom transfer (HAT). Mechanistic deuterium‐labeling studies have provided insight into outcome process. addition, cyclobutanes then demonstrated useful selective oxidation processes resulting cyclobutanones γ‐lactones.

Language: Английский

Citations

1
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, Journal Year: 2023, Volume and Issue: 135(49)

Published: Oct. 19, 2023

Abstract 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(sp 2 )−C(sp 3 ) 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

3
Orthogonal sp3‐Ge/B Bimetallic Modules: Enantioselective Construction and Enantiospecific Cross‐Coupling DOI
Mengyu Xu, Weitao Jiang,

Ming‐Zhi Xia

et al.

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

0
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

Citations

0