Catalytic Asymmetric Hydrogenation of Tetrasubstituted Unsaturated Lactams: An Efficient Approach to Enantioenriched 3,4-Disubstituted Piperidines DOI
Congcong Yin,

Yingmin Pan,

Xumu Zhang

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(2), P. 675 - 680

Published: Jan. 10, 2022

Asymmetric hydrogenation of tetrasubstituted alkenes remains a formidable challenge in asymmetric catalysis. We report herein an unprecedented Rh-catalyzed enantioselective and diastereoselective easily accessed α,β-disubstituted unsaturated lactams to afford synthetically valuable chiral with 1,2-consecutive stereocenters. The reaction could be performed on the gram scale, products concisely transformed enantiomerically pure trans-3,4-disubstituted piperidines, which are prevalent structural units medicinal agents.

Language: Английский

Stereoselective amino alcohol synthesis via chemoselective electrocatalytic radical cross-couplings DOI

Jiawei Sun,

Shuanghu Wang, Kaid C. Harper

et al.

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 3, 2025

Language: Английский

Citations

5
Evolution in heterodonor P-N, P-S and P-O chiral ligands for preparing efficient catalysts for asymmetric catalysis. From design to applications DOI Creative Commons
Jèssica Margalef, Maria Biosca, Pol de la Cruz‐Sánchez

et al.

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 446, P. 214120 - 214120

Published: July 19, 2021

The success of phosphine-oxazoline ligands (PHOX) inspired the progress in P-oxazoline ligand families by modifying either backbone, electronic and/or steric properties phosphine group or exchanging to a phosphinite phosphite group. In this respect, structures chiral have become more diverse and new very efficient emerged, which improved catalytic performance some asymmetric transformations, with an increased versatility, both range reactions substrates/reagents. addition, most are synthesized from easily accessible amino alcohols, maintaining short synthetic route developed for PHOX ligands. New been replacing oxazoline functionality several other N-donor groups, e.g. imidazole, thiazole, oxazole, pyridine, etc., O- S-groups. This review offers critical overview utility these successful bidentate heterodonor P-N, P-O P-S applied metal-mediated processes. We illustrate how, through proper design, can be excellent source ligands, superior many than best C2-symmetric N,N P,P-ligands reported so far.

Language: Английский

Citations

64
Cobalt‐Catalyzed Chemo‐ and Enantioselective Hydrogenation of Conjugated Enynes DOI
Yanhua Hu, Zhenfeng Zhang, Yangang Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(31), P. 16989 - 16993

Published: June 1, 2021

Asymmetric hydrogenation is one of the most powerful methods for preparation single enantiomer compounds. However, chemo- and enantioselective relatively inert unsaturated group in substrates possessing multiple bonds remains a challenge. We herein report protocol highly conjugated enynes while keeping alkynyl bond intact. Mechanism studies indicate that accompanying Zn2+ generated from zinc reduction CoII complex plays critical role to initiate plausible CoI /CoIII catalytic cycle. This approach allows efficient generation chiral propargylamines (up 99.9 % ee 2000 S/C) further useful chemical transformations.

Language: Английский

Citations

59
Stereodivergent asymmetric hydrogenation of quinoxalines DOI Creative Commons
Chenguang Liu,

Xufang Liu,

Qiang Liu

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(9), P. 2585 - 2600

Published: May 31, 2023

Language: Английский

Citations

24
Unlocking Diverse π-Bond Enrichment Frameworks by the Synthesis and Conversion of Boronated Phenyldiethynylethylenes DOI

Jinhui Xie,

Wangyang Li, Yong Lu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 10167 - 10176

Published: March 27, 2024

The π-bond enrichment frameworks not only serve as a crucial building block in organic synthesis but also assume pivotal role the fields of materials science, biomedicine, photochemistry, and other related disciplines owing to their distinctive structural characteristics. incorporation various substituents into C═C double bonds tetrasubstituted alkenes is currently highly significant research area. However, with diverse on poses challenge achieving stereoselectivity. Here, we reported an efficient convergent route Cu-catalyzed borylalkynylation both symmetrical unsymmetrical 1,3-diynes, B2pin2, acetylene bromide construction boronated phenyldiethynylethylene (BPDEE) derivatives excellent chemo-, stereo-, regioselectivities. BPDEE could transform novel π-conjugated gem-diphenyldiethynylethylene (DPDEE), vinylphenyldiethynylethylene (VPDEE), phenyltriethynylethylene (PTEE) by stepwise process, which provides flexible platform for complex that were difficult synthesize previous methods. initial optical characterization revealed synthesized molecules exhibited aggregation-induced emission (AIE) properties, further establishes groundwork future applications enriches advances field functional research.

Language: Английский

Citations

15
Ligand-Governed Regio- and Enantioselective [2 + 2 + 2] Cycloaddition of 1,7-Enynes: Assembly of the Benzo[c]chromen-1-ol Backbone and Access to Enantioenriched Cannabinol Bioisostere DOI

King Hung Nigel Tang,

Taichi Kishi,

Natsuhiko Sugimura

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

We herein report a regioselective synthesis of the benzo[c]chromenol core via cationic rhodium-catalyzed [2 + 2 2] cycloaddition 1,7-enynes with tetrolic acid derivatives. With selection an appropriate ligand, both regioisomers could be obtained in excellent regiomeric ratio and enantiomeric excess. The regioselectivity was governed by different factors, which suggested computational studies. Furthermore, asymmetric axially chiral cannabinol bioisostere candidate achieved transformation from central chirality to axial chirality. Demonstration natural compound also depicted.

Language: Английский

Citations

1
Discovery of a Thioxanthone–TfOH Complex as a Photoredox Catalyst for Hydrogenation of Alkenes Using p‐Xylene as both Electron and Hydrogen Sources DOI
Wenjie Kang, Bo Li, Meng Duan

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(48)

Published: Sept. 15, 2022

Hydrogenation of alkenes is one the most fundamental transformations in organic synthesis, and widely used petrochemical, pharmaceutical, food industries. Although numerous hydrogenation methods have been developed, novel types catalysis with new mechanisms hydrogen sources are still desirable. Thioxanthone (TX) energy-transfer photoreactions, but rarely photoredox processes. Herein we show that a catalytic amount TfOH as co-catalyst can tune properties TX to make it catalyst highly enhanced oxidative capability carbonylated cheap petroleum industrial product p-xylene serving source. Deuterium also be introduced by this method using D2 O D To best our knowledge, first example

Language: Английский

Citations

35
P-Stereogenic Ir-MaxPHOX: A Step toward Privileged Catalysts for Asymmetric Hydrogenation of Nonchelating Olefins DOI Creative Commons
Maria Biosca, Pol de la Cruz‐Sánchez, Jorge Faiges

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(5), P. 3020 - 3035

Published: Feb. 14, 2023

The Ir-MaxPHOX-type catalysts demonstrated high catalytic performance in the hydrogenation of a wide range nonchelating olefins with different geometries, substitution patterns, and degrees functionalization. These air-stable readily available have been successfully applied asymmetric di-, tri-, tetrasubstituted (ee′s up to 99%). combination theoretical calculations deuterium labeling experiments led uncovering factors responsible for enantioselectivity observed reaction, allowing rationalization most suitable substrates these Ir-catalysts.

Language: Английский

Citations

22
Cyclolignan synthesis streamlined by enantioselective hydrogenation of tetrasubstituted olefins DOI
Wenxiu Xu, Zhuo Peng,

Qing‐Xiu Gu

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(8), P. 986 - 997

Published: June 20, 2024

Language: Английский

Citations

7
Diastereoselective Hydrogenation of Tetrasubstituted Olefins using a Heterogeneous Pt‐Ni Alloy Catalyst DOI Creative Commons

William A. Swann,

Anish Yadav,

Nicholas B. Colvin

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: Feb. 26, 2024

Abstract Stereoselective hydrogenation of tetrasubstituted olefins is an attractive method to access compounds with two contiguous stereocenters. However, homogeneous catalysts for enantio‐ and diastereoselective exhibit low reactivity toward due steric crowding between the ligand scaffold substrate. Monometallic heterogeneous catalysts, on other hand, provide accessible surface active sites hindered but unpredictable inconsistent stereoinduction. In this work, we develop a Pt−Ni bimetallic alloy catalyst that can diastereoselectively hydrogenate unactivated, sterically‐bulky olefins, utilizing more oxophilic Ni atoms adsorb hydroxyl directing group direct facially‐selective hydrogen addition olefin via Pt atoms. Structure‐activity studies several compositions underscore importance exposing uniform PtNi achieve high diastereoselectivity minimize side reactions. The optimized Pt−Ni/SiO 2 exhibits good functional tolerance broad scope in cyclopentene scaffold, generating cyclopentanol products three synthetic utility demonstrated four‐step synthesis (1 R ,2 S )‐(+)‐ cis ‐methyldihydrojasmonate yield enantiopurity.

Language: Английский

Citations

5