Rhodium-Catalyzed Asymmetric Hydroselenation of 1-Alkynylindoles for Atroposelective Synthesis of Vinyl Selenoethers DOI

Yulong Kang,

Fen Wang, Xingwei Li

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(17), P. 13055 - 13064

Published: Aug. 15, 2024

Catalytic asymmetric hydrofunctionalization of π-bonds has been extensively studied, but the alkynes that affords atropoisometric products remains heavily underexplored. We herein report [Rh(COD)OAc]2/Mg(NTf2)2-catayzed highly atroposelective hydroselenation two classes 1-alkynylindoles using selenophenols, where Mg(II) salt both activates Rh catalyst and provides a key NTf2 anion essential for catalytic activity enantioselectivity, affording C–N axially chiral trisubstituted olefins bear relatively low racemization barrier (ΔG‡ ∼ 27 kcal/mol). The system features high activity, mild reaction conditions, good functional group tolerance, regio-, (E)-, enantioselectivity. selenoether moiety in product framework can be readily functionalized to give synthetically useful products.

Language: Английский

Transition-metal-catalyzed enantioselective C–N cross-coupling DOI
Jia Feng, Longlong Xi, Chuan‐Jun Lu

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(19), P. 9560 - 9581

Published: Jan. 1, 2024

Chiral amine scaffolds are among the most important building blocks in natural products, drug molecules, and functional materials, which have prompted chemists to focus more on their synthesis. Among accomplishments chiral synthesis, transition-metal-catalyzed enantioselective C-N cross-coupling is considered one of efficient protocols. This approach combines traditional C(sp

Language: Английский

Citations

10
Substituent-Controlled Regiodivergent Rearrangement of Gramine Ammonium Ylide DOI
Yu Shen,

Ao Huang,

Xiyao Lu

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

The complicated mechanism makes the regiodivergent rearrangement of ammonium ylide seem to be out reach. Herein, we reported a gramine well controlled by substituents. Density functional theory studies reveal that with more steric hindrance substituent 2-diazo-2-arylacetate goes through stepwise yield both kinetically and thermodynamically preferred [1,2]-rearrangement product. In contrast, less ethyl diazoacetate concerted generate [2,3]-rearrangement product, which is favored as result release ring strain in transition state. This study would open up avenues grasp ylide, will promote application skeletal editing synthesis complex natural products.

Language: Английский

Citations

1
Dual Catalytic C(sp2)–H Activation of Azaheterocycles toward C–N Atropisomers DOI
Juntao Sun, Yiyao Hu, Wen‐Ji He

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3700 - 3710

Published: Feb. 14, 2025

Language: Английский

Citations

1
Enantioselective synthesis of chiral N-arylpyrroles through photoinduced desymmetrization DOI Creative Commons

Zi‐Wei He,

Dong Liang, Jia‐Rong Chen

et al.

Green Synthesis and Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: March 1, 2025

Language: Английский

Citations

0
Rhodium(III)-Catalyzed Redox-Neutral [4 + 2] Annulation of 3,5-Diaryloxadiazoles with Alkynes: A Dual C–H Activation Strategy for Constructing C–N Atropisomers DOI
Siyuan Li, Yong Han, Zhen Yang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

A rhodium(III)-catalyzed dual-ring formation via cascade C-H activation/[4 + 2] annulation of 3,5-diaryoxadiazoles with alkynes was developed. This strategy has been demonstrated a variety 3,5-diaryloxadiazoles and alkynes, it successfully scaled up to gram-scale synthesis, highlighting its potential significance in the direct construction C-N atropisomers. Furthermore, cleavage N-O bond is essential for bicyclic structure absence an external oxidant. Mechanistic studies revealed that at 3-phenyl group oxadiazole likely rate-determining step this reaction.

Language: Английский

Citations

0
Rhodium-Catalyzed Asymmetric Hydroselenation of 1-Alkynylindoles for Atroposelective Synthesis of Vinyl Selenoethers DOI

Yulong Kang,

Fen Wang, Xingwei Li

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(17), P. 13055 - 13064

Published: Aug. 15, 2024

Catalytic asymmetric hydrofunctionalization of π-bonds has been extensively studied, but the alkynes that affords atropoisometric products remains heavily underexplored. We herein report [Rh(COD)OAc]2/Mg(NTf2)2-catayzed highly atroposelective hydroselenation two classes 1-alkynylindoles using selenophenols, where Mg(II) salt both activates Rh catalyst and provides a key NTf2 anion essential for catalytic activity enantioselectivity, affording C–N axially chiral trisubstituted olefins bear relatively low racemization barrier (ΔG‡ ∼ 27 kcal/mol). The system features high activity, mild reaction conditions, good functional group tolerance, regio-, (E)-, enantioselectivity. selenoether moiety in product framework can be readily functionalized to give synthetically useful products.

Language: Английский

Citations

3