Rhodium-Catalyzed Enantioselective Hydrosilylation of 1,1-Disubstituted Enamides DOI

Junhan Ma,

Chen-Li Jin,

Samuel Couve‐Bonnaire

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 8, 2024

Catalytic hydrosilylation of 1,1-disubstituted enamides is one the most challenging and synthetically useful processes in organosilicon chemistry asymmetric catalysis. Herein, we report a rhodium-catalyzed enantioselective α-arylenamides with substituted hydrosilanes aid chiral P-ligand, including newly developed spirophosphite ligands, giving various β-silylated amides excellent yields good to enantioselectivities (98:2 er after recrystallization). In addition, amines can be obtained by further functionalization product.

Language: Английский

Decatungstate-Catalyzed Hydrosilylation of α-Trifluoromethylalkenes for Construction of α-Trifluoromethyl-β-silanes DOI
M. Xiao,

Yidong Lang,

Ziqiang Cheng

et al.

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

Published: April 18, 2025

The hydrosilylation of alkenes is a pivotal transformation for the synthesis organosilanes; however, fluorine-containing limited due to facile β-fluoride elimination. Herein, by employing direct hydrogen atom transfer (HAT) catalyst, tetrabutylammonium decatungstate (TBADT), and using disulfide as co-catalyst, we have successfully developed mild photocatalytic α-trifluoromethylalkenes α-trifluoromethyl-β-silanes. Our method features conditions, good regioselectivity, compatibility. elimination was fully inhibited. A radical mechanism proposed based on preliminary results.

Language: Английский

Citations

0
Transition‐Metal‐Free Carbonyl Reduction and Hydrodefluorination of β‐Trifluoromethyl Enones with Hydrosilanes: Synthesis of gem‐Difluorovinyl Alcohols DOI

Peng‐Yuan Zhang,

Ya‐Fei Hu,

Jia‐Hao Chu

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(23)

Published: April 20, 2024

Abstract A tandem carbonyl reduction and hydrodefluorination of β‐trifluoromethyl enones with hydrosilanes under transition‐metal‐free conditions was developed for the synthesis a variety valuable gem ‐difluorovinyl alcohols. The hydrosilane could act as both reductive agent C(sp 3 )‐F bond‐breaking promoter mild reaction conditions. Synthetically useful organofluorides, such ‐fluorophosphine alkene, ketone, fluorinated dihydrofuran derivatives be readily constructed by further transformations obtained Moreover, method features conditions, operational simplicity, excellent functional group tolerance, scalability.

Language: Английский

Citations

2
Creation of a Chiral All-Carbon Quaternary Center Induced by CF3 and CH3 Substituents via Cu-Catalyzed Asymmetric Conjugate Addition DOI Creative Commons

Taiyo Yamamoto,

Masayuki Asakura,

Ken Yamanomoto

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(25), P. 5312 - 5317

Published: June 13, 2024

Cu-catalyzed asymmetric construction of a chiral quaternary center bearing CH3 and CF3 groups was achieved with high to excellent enantioselectivity using our originally developed ligands. The conjugate addition Me3Al β-CF3-substituted enones unsaturated ketoesters proceeded efficiently. use gives optically active furanones in yields enantioselectivities. perfluoroalkyl-substituted enone does not seem be favorable the present reaction.

Language: Английский

Citations

2
Ruthenium-Catalyzed Meta-Selective Trifluoroisopropylation of Arenes DOI

Shuxiong Han,

Min Liang,

Wenjie Ju

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(12), P. 8601 - 8609

Published: June 5, 2024

This work reports the mild and efficient Ru-catalyzed trifluoroisopropylation of arenes using 2-bromo-1,1,1-trifluoropropane. Various bioactive molecules, such as purine nucleoside derivatives, were well-suited for this transformation, affording corresponding products in moderate-to-good yields. method provides an strategy synthesizing trifluoroisopropyl molecules drug discovery.

Language: Английский

Citations

1
Transition-Metal-Free Hydrodefluoroamination of Trifluoromethyl Enones for the Synthesis of α-Fluoroenamides DOI

Ya‐Fei Hu,

M Kellis,

Ming-Yao Tang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(14), P. 10299 - 10310

Published: July 2, 2024

A three-component strategy was developed to enable hydrodefluoroamination of β-trifluoromethyl enones by selectively activating two C(sp3)-F bonds in the trifluoromethyl group. The method involved a sequence carbonyl reduction, hydrodefluorination, and defluoroamination under transition-metal-free conditions. Synthetically useful (E)-stereospecific α-fluoroenamides were obtained good yields with diverse functional group tolerance, which could be easily transformed into valuable organofluorides heterocycles. auxiliary exerts both electronic steric impacts on CF3-alkenes, allowing for controllable selective defluorination.

Language: Английский

Citations

0
Rhodium-Catalyzed Enantioselective Hydrosilylation of 1,1-Disubstituted Enamides DOI

Junhan Ma,

Chen-Li Jin,

Samuel Couve‐Bonnaire

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 8, 2024

Catalytic hydrosilylation of 1,1-disubstituted enamides is one the most challenging and synthetically useful processes in organosilicon chemistry asymmetric catalysis. Herein, we report a rhodium-catalyzed enantioselective α-arylenamides with substituted hydrosilanes aid chiral P-ligand, including newly developed spirophosphite ligands, giving various β-silylated amides excellent yields good to enantioselectivities (98:2 er after recrystallization). In addition, amines can be obtained by further functionalization product.

Language: Английский

Citations

0