Copper‐Catalyzed Enantioselective Doyle–Kirmse Reaction of Azide‐Ynamides via α‐Imino Copper Carbenes DOI
Xin Liu, Li‐Gao Liu,

Can‐Ming Chen

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(10)

Published: Jan. 14, 2023

Abstract [2,3]‐Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle–Kirmse reaction) generated from metal carbenes represents one of the powerful methods for construction C(sp 3 )−S and C−C bonds. Although significant advances have been achieved, asymmetric versions via generation ylides rarely reported to date, they so far limited diazo compounds as carbene precursors. Here, we describe a copper‐catalyzed enantioselective Doyle–Kirmse azide‐ynamide cyclization, leading practical divergent assembly an array chiral [1,4]thiazino[3,2‐ b ]indoles bearing quaternary carbon stereocenter in generally moderate excellent yields enantioselectivities. Importantly, this protocol unique catalytic non‐diazo approach unprecedented [2,3]‐sigmatropic α‐imino carbenes.

Language: Английский

Copper‐Catalyzed Enantioselective Doyle–Kirmse Reaction of Azide‐Ynamides via α‐Imino Copper Carbenes DOI
Xin Liu, Li‐Gao Liu,

Can‐Ming Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 14, 2023

[2,3]-Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle-Kirmse reaction) generated from metal carbenes represents one of the powerful methods for construction C(sp3 )-S and C-C bonds. Although significant advances have been achieved, asymmetric versions via generation ylides rarely reported to date, they so far limited diazo compounds as carbene precursors. Here, we describe a copper-catalyzed enantioselective Doyle-Kirmse azide-ynamide cyclization, leading practical divergent assembly an array chiral [1,4]thiazino[3,2-b]indoles bearing quaternary carbon stereocenter in generally moderate excellent yields enantioselectivities. Importantly, this protocol unique catalytic non-diazo approach unprecedented [2,3]-sigmatropic α-imino carbenes.

Language: Английский

Citations

30
Gold(I)‐Catalyzed Benzylic C(sp3)−H Functionalizations: Divergent Synthesis of Indole[a]‐ and [b]‐Fused Polycycles** DOI
Luca C. Greiner, Norihito Arichi, Shinsuke Inuki

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(3)

Published: Oct. 18, 2022

Abstract Phenyl azides substituted by an (alkylphenyl)ethynyl group facilitate benzylic sp 3 (C−H) functionalization in the presence of a JohnPhosAu catalyst, resulting indole‐fused tetra‐ and pentacycles via divergent N ‐ or C ‐cyclization. The chemoselectivity is influenced depending on counter‐anion, electron density α‐imino gold(I) carbene, alkyl groups stabilizing carbocation originating from 1,5‐hydride shift. An isotopic labeling experiment demonstrates involvement indolylgold(I) species tautomerization that much faster than deauration. formation leading to seven‐membered ring also demonstrated.

Language: Английский

Citations

26
Electronic and Steric Effects in a Gold(I)‐Catalyzed Intramolecular C(sp3)−H Bond Activation Reaction of 1‐Bromoalkynes DOI Creative Commons

Rubén Miguélez,

Omar Arto,

Nina Semleit

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(4), P. 780 - 789

Published: Jan. 5, 2024

Abstract The functional group compatibility of our recently disclosed gold(I)‐catalyzed cycloisomerization 1‐bromoalkynes is studied in detail. Two main features are addressed, the minimum distances at which polar groups tolerated and influence both electronic steric effects on performance aryl ether derivatives. Moreover, robustness assessment experiments have been carried out shedding light factors dictating tolerance. In addition, reaction has applied to synthesis a key intermediate total natural product heterobifunctional molecule. DFT calculations shed mechanistic behind observed reactivity trends. On one hand, destabilization TS by proximity may hamper for proximal groups. other some not regardless their position due preferential coordination gold oxygen atom over alkyne, resulting presumably competitive catalyst deactivation pathways.

Language: Английский

Citations

3
Gold(I)‐Catalyzed Benzylic C(sp3)−H Functionalizations: Divergent Synthesis of Indole[a]‐ and [b]‐Fused Polycycles** DOI
Luca C. Greiner, Norihito Arichi, Shinsuke Inuki

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 135(3)

Published: Oct. 18, 2022

Abstract Phenyl azides substituted by an (alkylphenyl)ethynyl group facilitate benzylic sp 3 (C−H) functionalization in the presence of a JohnPhosAu catalyst, resulting indole‐fused tetra‐ and pentacycles via divergent N ‐ or C ‐cyclization. The chemoselectivity is influenced depending on counter‐anion, electron density α‐imino gold(I) carbene, alkyl groups stabilizing carbocation originating from 1,5‐hydride shift. An isotopic labeling experiment demonstrates involvement indolylgold(I) species tautomerization that much faster than deauration. formation leading to seven‐membered ring also demonstrated.

Language: Английский

Citations

3
Copper‐Catalyzed Enantioselective Doyle–Kirmse Reaction of Azide‐Ynamides via α‐Imino Copper Carbenes DOI
Xin Liu, Li‐Gao Liu,

Can‐Ming Chen

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(10)

Published: Jan. 14, 2023

Abstract [2,3]‐Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle–Kirmse reaction) generated from metal carbenes represents one of the powerful methods for construction C(sp 3 )−S and C−C bonds. Although significant advances have been achieved, asymmetric versions via generation ylides rarely reported to date, they so far limited diazo compounds as carbene precursors. Here, we describe a copper‐catalyzed enantioselective Doyle–Kirmse azide‐ynamide cyclization, leading practical divergent assembly an array chiral [1,4]thiazino[3,2‐ b ]indoles bearing quaternary carbon stereocenter in generally moderate excellent yields enantioselectivities. Importantly, this protocol unique catalytic non‐diazo approach unprecedented [2,3]‐sigmatropic α‐imino carbenes.

Language: Английский

Citations

0