Palladium-Catalyzed Asymmetric Hydrophosphination of Internal Alkynes: Highly Regio- and Stereoselective Construction of Axially Chiral Phosphines DOI Creative Commons

Danqing Ji,

Jierui Jing,

Yi Wang

et al.

Published: Dec. 24, 2021

Palladium-catalyzed unprecedented atroposelective hydrophosphination of internal alkynes has been realized using diarylphosphines, affording C-N axially chiral trisubstituted olefins (vinylphosphines) in excellent regioselectiviry, (E)-selectivity, and enantioselectivity. The axial chirality was established via integration dynamic kinetic transformation the alkynes, with both symmetrical nonsymmetrical secondary phosphines being applicable. In latter case, additional P-central constructed good diastereoselectivity.

Language: Английский

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

138
Organocatalytic Enantioselective Synthesis of Axially ChiralN,N′‐Bisindoles DOI

Zhi‐Han Chen,

Tian‐Zhen Li,

Ning‐Yi Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(15)

Published: Feb. 7, 2023

This study establishes the first organocatalytic enantioselective synthesis of axially chiral N,N'-bisindoles via phosphoric acid-catalyzed formal (3+2) cycloadditions indole-based enaminones as novel platform molecules with 2,3-diketoesters, where de novo indole-ring formation is involved. Using this new strategy, various were synthesized in good yields and excellent enantioselectivities (up to 87 % yield 96 ee). More importantly, class exhibited some degree cytotoxicity toward cancer cells was derived into phosphine ligands high catalytic activity. provides a strategy for using asymmetric organocatalysis realize applications such scaffolds medicinal chemistry catalysis.

Language: Английский

Citations

90
Enantioselective Synthesis of N−N Bisindole Atropisomers DOI
Peng Zhang, Qi Xu, Xiaomei Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(44)

Published: Sept. 15, 2022

N-N Atropisomers are a common motif in natural products and represent significant dimension for exploration modern pharmaceutical medicinal chemistry. However, the catalytic atroposelective synthesis of such molecules remains challenging, hampering meaningful development. In particular, an enantioselective bisindole atropisomers is unprecedented. Herein, first via palladium-catalyzed de novo construction one indole skeleton presented. A wide variety axially chiral bisindoles were generated good yields with excellent enantioselectivities cascade condensation/N-arylation reaction. Structurally diverse indole-pyrrole, indole-carbazole, non-biaryl-indole possessing axis accessed using this protocol. Moreover, investigations density functional theory (DFT) calculations provided insight into reaction mechanism enantiocontrol.

Language: Английский

Citations

76
Modular Construction of Heterobiaryl Atropisomers and Axially Chiral Styrenes via All‐Carbon Tetrasubstituted VQMs DOI

Bo‐Bo Gou,

Yue Tang,

Yanhong Lin

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(40)

Published: Aug. 12, 2022

Here we report a new type of chiral all-carbon tetrasubstituted VQMs generated via phosphoric acids catalyzed nucleophilic addition 2-alkynylnaphthols to o-quinone methides or imines, which can be captured intramolecularly as result cycloaddition reaction. A class naphthyl-2H-chromenes bearing axially and centrally elements quinone-naphthols were prepared efficiently with good excellent yields, diastereoselectivities enantioselectivities. Noteworthy, the enantioselective alkynylnaphthols proceeded [2+2] cycloaddition, followed by retro-4π-electrocyclization 6π re-cyclization. While imines sequential [2+4] an auto oxidation Moreover, obtained naphthols converted into valuable phosphine ligands other functional molecules.

Language: Английский

Citations

54
Catalytic Atroposelective Electrophilic Amination of Indoles DOI

Jingyang Qin,

Tong Zhou, Tai‐Ping Zhou

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 25, 2022

Abstract Reported here is the first catalytic atroposelective electrophilic amination of indoles, which delivers functionalized atropochiral N ‐sulfonyl‐3‐arylaminoindoles with excellent optical purity. This reaction was furnished by 1,6‐nucleophilic addition to p ‐quinone diimines. Control experiments suggest an ionic mechanism that differs from radical pathway commonly proposed for 1,6‐addition quinones. The origin selectivity investigated through computational studies. Preliminary studies show obtained 3‐aminoindoles atropisomers exhibit anticancer activities. method valuable respect enlarging toolbox amine derivatives.

Language: Английский

Citations

38
Asymmetric Construction of an Aryl‐Alkene Axis by Palladium‐Catalyzed Suzuki–Miyaura Coupling Reaction DOI

Sheng‐Qi Qiu,

Yu Chen,

Xiang‐Jun Peng

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(45)

Published: Sept. 16, 2022

The application of Suzuki-Miyaura coupling reaction to forge the atropisomeric biaryls has seen remarkable progress but exploration this chemistry directly chiral C(aryl)-C(alkene) axis is underdeveloped. replacement arene substrates by alkenes intensifies challenges in terms reactivity, configurational atropostability product and selectivity control. By meticulous ligand design fine-tuning parameters, we identified a highly active 3,3'-triphenylsilyl-substituted phosphite realize arene-alkene hindered aryl halides vinyl boronates under very mild conditions. axially acyclic aryl-alkenes were generated commendable efficiency, enantioselectivity E/Z selectivity.

Language: Английский

Citations

37
Enantioselective Synthesis of Axially Chiral Styrene‐Carboxylic Esters by Rhodium‐Catalyzed Chelation‐Controlled [2+2+2] Cycloaddition DOI

Daisuke Yokose,

Yuki Nagashima,

Suzuka Kinoshita

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(23)

Published: March 17, 2022

Axially chiral styrene-carboxylic esters were synthesized in high yields with excellent enantioselectivity by the cationic rhodium(I)/H8 -BINAP complex-catalyzed chelation-controlled [2+2+2] cycloaddition reactions of 1,6- and 1,7-diynes 1,3-enyne-carboxylic esters. The diastereo- enantioselective synthesis C2 symmetric axially cis trans-stilbene-dicarboxylic was also achieved double two molecules 1,6-diyne 2,3-dialkynylmaleate 2,3-dialkynylfumarate, respectively. In these reactions, coordinating to rhodium a five-membered chelate more reactive than those six-membered chelate, although both chelation modes realized enantioselectivity. enantioselection mechanism rhodium(I)-catalyzed elucidated DFT calculations.

Language: Английский

Citations

33
Asymmetric catalysis with chiral cyclopentadienyl complexes to access privileged scaffolds DOI
Caitlin Davies, Saad Shaaban, Herbert Waldmann

et al.

Trends in Chemistry, Journal Year: 2022, Volume and Issue: 4(4), P. 318 - 330

Published: Feb. 5, 2022

Language: Английский

Citations

26
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, Journal Year: 2022, Volume and Issue: 134(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

15
Catalytic Atroposelective Electrophilic Amination of Indoles DOI

Jingyang Qin,

Tong Zhou, Tai‐Ping Zhou

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(31)

Published: May 25, 2022

Abstract Reported here is the first catalytic atroposelective electrophilic amination of indoles, which delivers functionalized atropochiral N ‐sulfonyl‐3‐arylaminoindoles with excellent optical purity. This reaction was furnished by 1,6‐nucleophilic addition to p ‐quinone diimines. Control experiments suggest an ionic mechanism that differs from radical pathway commonly proposed for 1,6‐addition quinones. The origin selectivity investigated through computational studies. Preliminary studies show obtained 3‐aminoindoles atropisomers exhibit anticancer activities. method valuable respect enlarging toolbox amine derivatives.

Language: Английский

Citations

10