Dual‐Catalytic Structural Isomerisation as a Route to α‐Arylated Ketones DOI Creative Commons

Danijela Lunic,

Nikita Vystavkin,

Jingyang Qin

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 9, 2024

Abstract Isomerisation reactions provide streamlined routes to organic compounds which are otherwise hard directly synthesise. The most common forms positional, geometrical or stereochemical isomerisations involve the relocation of a double bond change in relative location groups space. In contrast, far fewer examples structural (or constitutional) isomerisation exist where connectivity between atoms is altered. development platforms capable such rearrangement poses unique set challenges because chemical bonds must be selectively cleaved, and new ones formed without overall addition removal atoms. Here, we show that dual catalytic system can enable readily available allylic alcohols into more challenging‐to‐synthesise α‐arylated ketones via H‐atom transfer initiated semi‐pinacol rearrangement. Key our strategy combination cobalt catalyst photocatalyst under reductive, protic conditions allows intermediates propagate turnover. By providing an unusual disconnection motifs difficult access through direct arylation, anticipate inspiring other advanced strategies will further retrosynthetic logic for complex molecule synthesis.

Language: Английский

Photoexcited Hantzsch Ester and Cobalt Catalysis Enable Diastereo- and Enantioselective Allylation of Aldehydes DOI

Junjie Xue,

Jiaming Zou,

Shen Gao

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6165 - 6172

Published: April 2, 2025

Language: Английский

Citations

0
Allenyl Carbonate as a Butadiene Surrogate in Cobalt-Catalyzed Crotylation of Aldehydes DOI

Subhankar Pradhan,

Priyanka Chakraborty,

Soumen Paira

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(9), P. 5893 - 5899

Published: April 18, 2023

Allenyl carbonate was used as a 1,3-butadiene surrogate to develop photocatalytically sustainable protocol for cobalt-catalyzed crotylation of aldehydes. The developed method tolerated wide range aromatic and aliphatic aldehydes with retention functional groups under mild conditions produced good-to-excellent yields crotylated secondary alcohols. Based on preliminary mechanistic studies literature precedents, plausible mechanism is proposed.

Language: Английский

Citations

7
A computational study on cobalt-catalyzed allylic substitution of racemic allylic carbonates with amines: inner-sphere C–N reductive elimination and origins of regio- and enantioselectivities DOI

Zhen Shen,

Hongli Wu, Jinjin Yang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(12), P. 2976 - 2987

Published: Jan. 1, 2023

DFT calculations reveal an inner-sphere C–N reductive elimination pathway for the cobalt/bisoxazolinephosphine-catalyzed allylic substitution of racemic carbonates with amines.

Language: Английский

Citations

7
Developing Organometallic Nucleophilic Reagents Via Photoredox Catalysis DOI
Andrea Gualandi, Pier Giorgio Cozzi, Francesco Calogero

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 55(22), P. 3737 - 3758

Published: June 7, 2023

Abstract The addition of organometallic reagents to the carbonyl group represents a key transformation, both in academia and industry. Most these transformations rely on mechanism which accessible reactive halides are transformed into corresponding nucleophilic compounds through redox mechanism, using metal (Cr, Mg, In, etc.) low oxidation state, by electron transfer. With advent photoredox catalysis, formation radicals, or reduction suitable tailored organic precursors, was merged with transition catalysis. By radical-to-polar crossover (RPCO­), radical is combined an produce, via radical-radical trapping, polar reagent. Using dual catalysis (metallaphotoredox catalysis), reagent can be prepared, avoiding use metals state. Herein, description results obtained our contributions others connection between radical-based photochemistry, we provide core guidance for further synthetic developments. We anticipate that extending strategy beyond Barbier reactions described here, taming less-activated carbonyls, studying other important electrophiles, will soon realize breakthroughs. 1 Introduction 2 Photoredox Catalysis: A Survival Guide ‘Photo-Curious’ 3 Chromium Nucleophilic Organometallic Reagents 3.1 Allylation Aldehydes 3.2 Dienes 3.3 Propargylation 1,3-Enynes 3.4 Alkenylation 3.5 Alkylation 3.6 Enantioselective Chromium-Mediated Reactions 4 Titanium 4.1 4.2 4.3 4.4 Benzylation 4.5 5. Cobalt 5.1 6 Conclusion

Language: Английский

Citations

7
Dual‐Catalytic Structural Isomerisation as a Route to α‐Arylated Ketones DOI Creative Commons

Danijela Lunic,

Nikita Vystavkin,

Jingyang Qin

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 9, 2024

Abstract Isomerisation reactions provide streamlined routes to organic compounds which are otherwise hard directly synthesise. The most common forms positional, geometrical or stereochemical isomerisations involve the relocation of a double bond change in relative location groups space. In contrast, far fewer examples structural (or constitutional) isomerisation exist where connectivity between atoms is altered. development platforms capable such rearrangement poses unique set challenges because chemical bonds must be selectively cleaved, and new ones formed without overall addition removal atoms. Here, we show that dual catalytic system can enable readily available allylic alcohols into more challenging‐to‐synthesise α‐arylated ketones via H‐atom transfer initiated semi‐pinacol rearrangement. Key our strategy combination cobalt catalyst photocatalyst under reductive, protic conditions allows intermediates propagate turnover. By providing an unusual disconnection motifs difficult access through direct arylation, anticipate inspiring other advanced strategies will further retrosynthetic logic for complex molecule synthesis.

Language: Английский

Citations

2