A Pd−H/Isothiourea Cooperative Catalysis Approach to anti‐Aldol Motifs: Enantioselective α‐Alkylation of Esters with Oxyallenes** DOI Creative Commons

Hua‐Chen Lin,

Gary J. Knox,

Colin M. Pearson

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(25)

Published: March 21, 2022

Abstract The biological and therapeutic significance of natural products is a powerful impetus for the development efficient methods to facilitate their construction. Accordingly, reflecting prevalence β‐oxy‐carbonyl motifs, sophisticated arsenal aldol‐based strategies has evolved that contingent on generation single enolate isomers. Since this potential compromise efficiency in reagent‐based paradigms, direct catalysis‐based solutions would be enabling. To complement array substrate‐based strategies, regulate geometry at catalyst level, catalytic alkylation esters with oxyallenes been developed. Synergizing metal hydride reactivity Lewis base catalysis resulted broad reaction scope useful levels stereocontrol (up >99 % ee ). Facile derivatization these ambiphilic linchpins demonstrated, providing access high‐value vicinal stereocenter‐containing including 1,2‐amino alcohols.

Language: Английский

Enantioselective Palladium‐Catalyzed Hydrophosphinylation of Allenes with Phosphine Oxides: Access to Chiral Allylic Phosphine Oxides DOI
Zhiping Yang, Jun Wang

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(52), P. 27288 - 27292

Published: Sept. 28, 2021

Abstract A Pd‐catalyzed hydrophosphinylation of alkyl and aryl‐oxyallenes with phosphine oxides has been developed for the efficient rapid construction a family chiral allylic diverse range functional groups. This methodology was further applied in facile 2 H ‐chromene later stage functionalization cholesterol.

Language: Английский

Citations

77
Diastereodivergent Aldol‐Type Coupling of Alkoxyallenes with Pentafluorophenyl Esters Enabled by Synergistic Palladium/Chiral Lewis Base Catalysis DOI
Minghui Zhu, Peixin Wang, Qinglong Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(33)

Published: June 17, 2022

As a fundamental and synthetically useful C-C bond formation reaction, the aldol reaction is one of most versatile transformations in organic synthesis. However, despite extensive research on asymmetric versions unified method for stereoselective access to complementary syn anti diastereomeric products remains be developed. In this study, we developed synergistic palladium/chiral Lewis base system that overcomes inherent diastereoselectivity bias reactions and, as result, allowed us achieve first diastereodivergent coupling alkoxyallenes with pentafluorophenol esters. Computational studies suggest mechanism involving an intermolecular protonative hydropalladation pathway rather than palladium-hydride migratory insertion pathway. The origin stereochemistry catalysis rationalized by DFT calculations.

Language: Английский

Citations

65
A Pd−H/Isothiourea Cooperative Catalysis Approach to anti‐Aldol Motifs: Enantioselective α‐Alkylation of Esters with Oxyallenes** DOI Creative Commons

Hua‐Chen Lin,

Gary J. Knox,

Colin M. Pearson

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(25)

Published: March 21, 2022

Abstract The biological and therapeutic significance of natural products is a powerful impetus for the development efficient methods to facilitate their construction. Accordingly, reflecting prevalence β‐oxy‐carbonyl motifs, sophisticated arsenal aldol‐based strategies has evolved that contingent on generation single enolate isomers. Since this potential compromise efficiency in reagent‐based paradigms, direct catalysis‐based solutions would be enabling. To complement array substrate‐based strategies, regulate geometry at catalyst level, catalytic alkylation esters with oxyallenes been developed. Synergizing metal hydride reactivity Lewis base catalysis resulted broad reaction scope useful levels stereocontrol (up >99 % ee ). Facile derivatization these ambiphilic linchpins demonstrated, providing access high‐value vicinal stereocenter‐containing including 1,2‐amino alcohols.

Language: Английский

Citations

35
Enantioselective Palladium‐Catalyzed Hydrophosphinylation of Allenes with Phosphine Oxides: Access to Chiral Allylic Phosphine Oxides DOI
Zhiping Yang, Jun Wang

Angewandte Chemie, Journal Year: 2021, Volume and Issue: 133(52), P. 27494 - 27498

Published: Sept. 28, 2021

Abstract A Pd‐catalyzed hydrophosphinylation of alkyl and aryl‐oxyallenes with phosphine oxides has been developed for the efficient rapid construction a family chiral allylic diverse range functional groups. This methodology was further applied in facile 2 H ‐chromene later stage functionalization cholesterol.

Language: Английский

Citations

19
Diastereodivergent Aldol‐Type Coupling of Alkoxyallenes with Pentafluorophenyl Esters Enabled by Synergistic Palladium/Chiral Lewis Base Catalysis DOI
Minghui Zhu, Peixin Wang, Qinglong Zhang

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(33)

Published: June 17, 2022

Abstract As a fundamental and synthetically useful C−C bond formation reaction, the aldol reaction is one of most versatile transformations in organic synthesis. However, despite extensive research on asymmetric versions unified method for stereoselective access to complementary syn anti diastereomeric products remains be developed. In this study, we developed synergistic palladium/chiral Lewis base system that overcomes inherent diastereoselectivity bias reactions and, as result, allowed us achieve first diastereodivergent coupling alkoxyallenes with pentafluorophenol esters. Computational studies suggest mechanism involving an intermolecular protonative hydropalladation pathway rather than palladium‐hydride migratory insertion pathway. The origin stereochemistry catalysis rationalized by DFT calculations.

Language: Английский

Citations

11
A Pd−H/Isothiourea Cooperative Catalysis Approach to anti‐Aldol Motifs: Enantioselective α‐Alkylation of Esters with Oxyallenes** DOI Creative Commons

Hua‐Chen Lin,

Gary J. Knox,

Colin M. Pearson

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(25)

Published: March 21, 2022

Abstract The biological and therapeutic significance of natural products is a powerful impetus for the development efficient methods to facilitate their construction. Accordingly, reflecting prevalence β‐oxy‐carbonyl motifs, sophisticated arsenal aldol‐based strategies has evolved that contingent on generation single enolate isomers. Since this potential compromise efficiency in reagent‐based paradigms, direct catalysis‐based solutions would be enabling. To complement array substrate‐based strategies, regulate geometry at catalyst level, catalytic alkylation esters with oxyallenes been developed. Synergizing metal hydride reactivity Lewis base catalysis resulted broad reaction scope useful levels stereocontrol (up >99 % ee ). Facile derivatization these ambiphilic linchpins demonstrated, providing access high‐value vicinal stereocenter‐containing including 1,2‐amino alcohols.

Language: Английский

Citations

2