Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage DOI
Casey B. Roos, Chang-Hwa Chiang, Lauren A. M. Murray

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(17), P. 10641 - 10727

Published: Aug. 28, 2023

Enantiomers, where chirality arises from restricted rotation around a single bond, are atropisomers. Due to the unique nature of origins their chirality, synthetic strategies access these compounds in an enantioselective manner differ those used prepare enantioenriched containing point arising unsymmetrically substituted carbon center. In particular stereodynamic transformations, such as dynamic kinetic resolutions, thermodynamic and deracemizations, which rely on ability racemize or interconvert enantiomers, promising set transformations optically pure late stage sequence. Translation approaches with atropisomers requires expanded toolbox for epimerization/racemization provides opportunity develop new conceptual framework synthesis compounds.

Language: Английский

Construction of axial chirality via asymmetric radical trapping by cobalt under visible light DOI
Xuan‐Feng Jiang, Wei Xiong, Shuang Deng

et al.

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(9), P. 788 - 797

Published: Sept. 15, 2022

Language: Английский

Citations

93
Traditional and sustainable approaches for the construction of C–C bonds by harnessing C–H arylation DOI Creative Commons
Jagrit Grover, Gaurav Prakash, Nupur Goswami

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Feb. 28, 2022

Abstract Biaryl scaffolds are found in natural products and drug molecules exhibit a wide range of biological activities. In past decade, the transition metal-catalyzed C–H arylation reaction came out as an effective tool for construction biaryl motifs. However, traditional reactions have limitations like harsh conditions, narrow substrate scope, use additives etc. therefore encouraged synthetic chemists to look alternate greener approaches. This review aims draw general overview on bond formation C–C bonds with aid different methodologies, majorly highlighting sustainable

Language: Английский

Citations

82
Catalytic Asymmetric Construction of Axially and Centrally Chiral Heterobiaryls by Minisci Reaction DOI
Dong Liang, Jia‐Rong Chen, Liping Tan

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(13), P. 6040 - 6049

Published: March 24, 2022

Axially chiral biaryls and heterobiaryls constitute the most represented subclass of atropisomers with prevalence in natural products, bioactive compounds, privileged ligand/catalysts, optically pure materials. Despite many ionic protocols for their construction, radical-based variants represent another highly desirable intriguing strategy but are far less developed. Moreover, efficient synthesis axially heterobiaryl molecules, especially ones having multiple heteroatoms other types elements, through radical routes remains extremely limited. We herein disclose first catalytic asymmetric, metal-free construction centrally by Minisci reaction 5-arylpyrimidines α-amino acid-derived redox-active esters. This is enabled use 4CzIPN as an organic photoredox catalyst conjunction a phosphoric acid catalyst. The achieved variety interesting featuring union α-branched amine generally excellent regio-, diastereo-, enantioselectivity (up to 82% yield; >19:1 dr; >99% ee). finding also builds up new platform development desymmetrization methods via radical-involved atroposelective functionalization at heteroarene prochiral heterobiaryls.

Language: Английский

Citations

77
Dynamic Kinetic Reductive Conjugate Addition for Construction of Axial Chirality Enabled by Synergistic Photoredox/Cobalt Catalysis DOI
Wei Xiong, Xuan‐Feng Jiang,

Wencheng Wang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(14), P. 7983 - 7991

Published: March 28, 2023

Conjugate addition is among the most important synthetic protocols for constructing carbon skeletons and widely used to synthesize natural products drugs. However, asymmetric catalysis studies have mainly focused on stereogenic centers arising from conjugate alkenes. Here, we report first photoinduced cobalt-catalyzed dynamic kinetic reductive reaction that enables formation of heterobiaryls with axial chirality (45 examples, up 91% yield 97% ee). This method features mild conditions, good functional-group tolerance, excellent enantiomeric control. Significantly, large amounts metal waste precious catalysts can be avoided under these conditions. Migration chiral arylcobalt species into alkene might rate-determining step based studies.

Language: Английский

Citations

59
Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage DOI
Casey B. Roos, Chang-Hwa Chiang, Lauren A. M. Murray

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(17), P. 10641 - 10727

Published: Aug. 28, 2023

Enantiomers, where chirality arises from restricted rotation around a single bond, are atropisomers. Due to the unique nature of origins their chirality, synthetic strategies access these compounds in an enantioselective manner differ those used prepare enantioenriched containing point arising unsymmetrically substituted carbon center. In particular stereodynamic transformations, such as dynamic kinetic resolutions, thermodynamic and deracemizations, which rely on ability racemize or interconvert enantiomers, promising set transformations optically pure late stage sequence. Translation approaches with atropisomers requires expanded toolbox for epimerization/racemization provides opportunity develop new conceptual framework synthesis compounds.

Language: Английский

Citations

51