Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(12), P. 3647 - 3647
Published: Jan. 1, 2024
Language: Английский
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(31), P. 17018 - 17022
Published: July 27, 2023
Alkene difunctionalizations enable the synthesis of structurally elaborated products from simple and ubiquitous starting materials in a single chemical step. Carbohydroxylations olefins represent family reactivity that furnish complex alcohols. While examples this type three-component coupling have been reported, catalytic asymmetric remain elusive. Here, we report an enzyme-catalyzed carbohydroxylation alkenes catalyzed by flavin-dependent "ene"-reductases to produce enantioenriched tertiary Seven rounds protein engineering reshape enzyme's active site increase activity enantioselectivity. Mechanistic studies suggest C–O bond formation occurs via 5-endo-trig cyclization with pendant ketone afford α-oxy radical which is oxidized hydrolyzed form product. This work demonstrates photoenzymatic reactions involving can terminate radicals mechanisms other than hydrogen atom transfer, expanding their utility synthesis.
Language: Английский
Citations
18
Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(9), P. 2477 - 2484
Published: Jan. 1, 2024
A variety of optically active tertiary propargylic alcohols and tetrasubstituted 2,3-allenoic acids have been synthesized via a Pd(( R )-DTBM-SEGphos)Cl 2 -catalyzed carboxylative kinetic resolution reaction racemic alcohols.
Language: Английский
Citations
5
Organic Letters, Journal Year: 2024, Volume and Issue: 26(3), P. 702 - 707
Published: Jan. 11, 2024
We report herein an efficient NHC-catalyzed kinetic resolution of acyclic tertiary propargylic alcohols that provides them in high to excellent enantioselectivity. This is the first example realized by enantioselective acylation. The recovered enantioenriched can be facilely converted into other valuable compounds such as densely functionalized and carbmates yields stereopurity. Density functional theory calculations were performed determine reaction mechanism understand origin enantiodiscrimination.
Language: Английский
Citations
4
Science Advances, Journal Year: 2025, Volume and Issue: 11(12)
Published: March 21, 2025
An efficient synthesis of chiral tertiary alcohols through asymmetric nucleophilic addition reaction aldehyde hydrazones to simple ketones (especially aryl/methyl ketones) has been well established. Aryl aldehydes could be used as latent benzyl carbanion equivalents via reductive polarity reversal. The key the success was combination an achiral monophosphine ligand Ph 2 P(2-furyl) with a diamine derivative, which enhanced enantioselectivity and reactivity. Density functional theory calculations revealed hydrogen bond interactions between ligand, base anion, combined induce desired enantioselectivity. Moreover, further synthetic transformation high chirality transfer also demonstrated.
Language: Английский
Citations
0
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: April 15, 2025
The integration of trifluoroacetyl (CF3CO) groups into organic skeletons is a key research topic in synthetic chemistry given their significant potential to boost biological activity. Despite recent developments strategies for incorporating moiety via radical intermediates, the practical utilization inexpensive and readily available trifluoroacetic acids as sources has not yet been developed. Herein, an electrochemical strategy employed achieve deoxygenative transformation directly with assistance PPh3. obtained radicals are then coupled sulfoximine species, thus enabling synthesis N-trifluoroacetylated sulfoximines. Additionally, other fluorinated alkyl carboxylic acids, including perfluoro-, difluoro-, trifluoromethylcarboxylic can also be efficiently utilized under these conditions, leading corresponding acylated Moreover, trifluoroacetylation drug-based molecules easy execution scale-up experiments highlight applicability this protocol.
Language: Английский
Citations
0
Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(6), P. 2016 - 2021
Published: March 1, 2024
Language: Английский
Citations
3
Chemical Science, Journal Year: 2023, Volume and Issue: 14(28), P. 7709 - 7715
Published: Jan. 1, 2023
A novel three-component protocol to synthesize trisubstituted allenes from 2-alkynyl-1,4-diol dicarbonate with organoboronic acid and malonate has been developed.
Language: Английский
Citations
8
Organic Letters, Journal Year: 2024, Volume and Issue: 26(29), P. 6279 - 6283
Published: July 18, 2024
2(3
Citations
2
The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(19), P. 13645 - 13654
Published: Sept. 8, 2023
A copper/PyBisulidine-catalyzed enantioselective alkynylation of electrophilic pyrazole-4,5-dione with terminal alkynes has been developed. Chiral tertiary propargylic alcohols bearing the pyrazolone motif were prepared yields (up to 99%) and enantioselectivities 99% ee). The prominent feature this protocol includes its mild reaction conditions good stereoselectivities. nonlinear effect study showed that catalytically active specie was a monomeric catalyst excess copper activated through π-system.
Language: Английский
Citations
4
Chem Catalysis, Journal Year: 2023, Volume and Issue: 4(1), P. 100859 - 100859
Published: Dec. 28, 2023
Language: Английский
Citations
4