Diastereo- and atroposelective synthesis of N-arylpyrroles enabled by light-induced phosphoric acid catalysis DOI Creative Commons
Lei Dai, Xueting Zhou, Jiami Guo

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 9, 2023

The C-N axially chiral N-arylpyrrole motifs are privileged scaffolds in numerous biologically active molecules and natural products, as well ligands/catalysts. Asymmetric synthesis of N-arylpyrroles, however, is still challenging, the simultaneous creation contiguous axial central chirality remains unknown. Herein, a diastereo- atroposelective N-arylpyrroles enabled by light-induced phosphoric acid catalysis has been developed. key transformation one-pot, three-component oxo-diarylation reaction, which simultaneously creates quaternary stereogenic center. A broad range unactivated alkynes were readily employed reaction partner this transformation, products obtained good yields, with excellent enantioselectivities very diastereoselectivities. Notably, skeletons represent interesting structural that could be used ligands catalysts asymmetric catalysis.

Language: Английский

Recent Advances in Catalytic Asymmetric Construction of Atropisomers DOI
Jun Kee Cheng, Shao‐Hua Xiang, Shaoyu Li

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(8), P. 4805 - 4902

Published: March 27, 2021

Atropisomerism is a stereochemical behavior portrayed by three-dimensional molecules that bear rotationally restricted σ bond. Akin to the well-represented point-chiral molecules, atropisomerically chiral compounds are finding increasing utilities in many disciplines where molecular asymmetry influential. This provides steady demand on atroposelective synthesis, numerous synthetic pursuits have been rewarded with conceptually novel and streamlined methods while expanding structural diversity of atropisomers. review summarizes key achievements stereoselective preparation biaryl, heterobiaryl, nonbiaryl atropisomers documented between 2015 2020. Emphasis placed strategies for each class, examples cited illustrate potential applications accessed atropochiral targets.

Language: Английский

Citations

748
Organocatalytic Atroposelective Synthesis of N−N Axially Chiral Indoles and Pyrroles by De Novo Ring Formation DOI

Ke‐Wei Chen,

Zhi‐Han Chen,

Shuang Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(17)

Published: Jan. 26, 2022

Abstract The first highly atroposelective construction of N−N axially chiral indole scaffolds was established via a new strategy de novo ring formation. This makes use the organocatalytic asymmetric Paal–Knorr reaction well‐designed N ‐aminoindoles with 1,4‐diketones, thus affording ‐pyrrolylindoles in high yields and excellent atroposelectivities (up to 98 % yield, 96 ee). In addition, this is applicable for synthesis bispyrroles 97 More importantly, such heterocycles can be converted into organocatalysts applications catalysis, some molecules display potent anticancer activity. work not only provides but also offers members atropisomer family promising synthetic medicinal chemistry.

Language: Английский

Citations

140
Enantioselective Synthesis of Atropisomers via Vinylidene ortho-Quinone Methides (VQMs) DOI
Wenling Qin, Yidong Liu, Hailong Yan

et al.

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(19), P. 2780 - 2795

Published: Sept. 19, 2022

ConspectusAtropisomers, arising from conformational restriction, are inherently chiral due to the intersecting dissymmetric planes. Since there numerous applications of enantiopure atropisomers in catalyst design, drug discovery, and material science, asymmetric preparation these highly prized molecules has become a flourishing field synthetic chemistry. A number catalysts, procedures, novel concepts have been developed for manufacture atropisomeric molecules. However, intrinsic properties different types featuring biaryl, hetero-biaryl, or non-biaryl architectures, only very few methods pass rigorous inspection considered generally applicable. The development broadly applicable strategy various is challenge. In this Account, we summarize our recent studies on enantioselective synthesis using vinylidene ortho-quinone methides (VQMs) as pluripotent intermediates.The most appealing features VQMs disturbed aromaticity axial chirality allene fragment. At outset, organic neglected their principal liabilities: ephemeral nature, extraordinary reactivity, multireaction sites. domestication transient intermediate was demonstrated by situ catalytic generation VQMs, reactivity selectivity were fully explored judiciously modifying precursors tuning systems. variety axially heterocycles achieved through five-, six-, seven- nine-membered ring formation VQM intermediates with kinds branched nucleophilic functional groups. C–N axis could be constructed via N-annulation desymmetrization preformed scaffolds. We take advantage high electrophilicity toward series sulfur carbon based nucleophiles leading vinyl arenes. Furthermore, helical compounds realized cycloaddition consecutive annulation intermediates. These achievements that work nuclear parent collective distinct complex optically active atropisomers. Recently, isolation structural characterization elusive which questioned putative decades. successful provided direct evidence existence an unprecedented opportunity directly investigate reactivity. good thermal stability reserved isolated great potential reagents expanded border

Language: Английский

Citations

132
Access to axially chiral styrenes via a photoinduced asymmetric radical reaction involving a sulfur dioxide insertion DOI
Chun Zhang,

Zhimei Tang,

Yanjie Qiu

et al.

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(1), P. 164 - 177

Published: Jan. 1, 2022

Language: Английский

Citations

80
Quinone methides and indole imine methides as intermediates in enantioselective catalysis DOI
Xingguang Li, Zhiyang Li, Jianwei Sun

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(6), P. 426 - 438

Published: June 6, 2022

Language: Английский

Citations

76
Carbene-catalyzed atroposelective synthesis of axially chiral styrenes DOI Creative Commons
Jia‐Lei Yan,

Rakesh Maiti,

Shi‐Chao Ren

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Jan. 10, 2022

Abstract Axially chiral styrenes bearing a axis between sterically non-congested acyclic alkene and an aryl ring are difficult to prepare due low rotational barrier of the axis. Disclosed here is N -heterocyclic carbene (NHC) catalytic asymmetric solution this problem. Our reaction involves ynals, sulfinic acids, phenols as substrates with NHC catalyst. Key steps involve selective 1,4-addition anion acetylenic acylazolium intermediate sequential E -selective protonation set up affords axially product > 99:1 e.r ., 20:1 / Z selectivity, excellent yields. The sulfone carboxylic ester moieties in our styrene products common bioactive molecules catalysis.

Language: Английский

Citations

75
Axially chiral alkenes: Atroposelective synthesis and applications DOI Creative Commons

San Wu,

Shao‐Hua Xiang, Jun Kee Cheng

et al.

Tetrahedron Chem, Journal Year: 2022, Volume and Issue: 1, P. 100009 - 100009

Published: March 1, 2022

Axial chirality is historically epitomized by biaryl compounds containing rotationally impeded aryl-aryl linkage. As the field of atroposelective catalysis advances, synthesis and application less common scaffolds such as alkenes have now come to fore. The manifestation axial in aryl was hypothesized 1928 first resolution achieved nearly a decade later. However, catalytic asymmetric construction axially chiral open-chain appeared only 2017 which ushered renewed focus on these structures. In principle, possess an alkene group tethered at one end stereogenic axis, greatly reduces overall rigidity. To date, atropisomers with C (vinyl)-C (aryl) (vinyl)-heteroatom bond been reported. Considering rapid growth synthetic utility alkenes, this review intends provide historical overview discusses new developments. It hope that timely discussion would motivate continued nascent field.

Language: Английский

Citations

74
Recent developments on 1,2-difunctionalization and hydrofunctionalization of unactivated alkenes and alkynes involving C–S bond formation DOI

Bo Dong,

Jian Shen, Lan‐Gui Xie

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(5), P. 1322 - 1345

Published: Jan. 1, 2023

Functionalization of alkenes/alkynes is a highly effective route to achieve molecular complexity. This review summarizes recent progresses on the 1,2-difunctionalization/hydrofunctionalization unactivated with C−S bond formation.

Language: Английский

Citations

68
Catalytic atroposelective synthesis DOI
Shao‐Hua Xiang, Wei‐Yi Ding, Yong‐Bin Wang

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(5), P. 483 - 498

Published: April 30, 2024

Language: Английский

Citations

39
Enantioselective Synthesis of Planar‐Chiral Sulfur‐Containing Cyclophanes by Chiral Sulfide Catalyzed Electrophilic Sulfenylation of Arenes DOI

Deng Zhu,

Tong Mu,

Ze‐Long Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 17, 2024

Abstract An efficient catalytic asymmetric electrophilic sulfenylation reaction for the synthesis of planar‐chiral sulfur‐containing cyclophanes has been developed first time. This was achieved by using a new Lewis base catalyst and ortho ‐trifluoromethyl‐substituted sulfenylating reagent. Using substrates with low rotational energy barrier, transformation proceeded through dynamic kinetic resolution, high barrier allowed to undergo resolution process. Meanwhile, this compatible desymmetrization process when symmetric were used. Various readily obtained in moderate excellent yields enantioselectivities (up 97 % yield 95 ee). approach used synthesize pharmaceutically relevant molecules. Density functional theory calculations showed that π‐π interactions between sulfenyl group aromatic ring substrate play crucial role enantioinduction reaction.

Language: Английский

Citations

22