Isoquinoline-Forming Staudinger–aza-Wittig Reaction Enabled by Atroposelective PIII/PIV=O Redox Catalysis DOI
Benjamin List,

Kateryna Kryvous

Synfacts, Journal Year: 2023, Volume and Issue: 19(11), P. 1143 - 1143

Published: Oct. 14, 2023

Key words Staudinger–aza-Wittig - QUINOX QUINAP atroposelectivity

Language: Английский

Atroposelective catalysis DOI

Tanno A. Schmidt,

Valeriia Hutskalova,

Christof Sparr

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 497 - 517

Published: June 18, 2024

Language: Английский

Citations

16
Chiral Bisphosphine-Catalyzed Asymmetric Staudinger/aza-Wittig Reaction: An Enantioselective Desymmetrizing Approach to Crinine-Type Amaryllidaceae Alkaloids DOI
Hongzhi Yang, Jingyang Zhang, Sen Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(20), P. 14136 - 14148

Published: April 20, 2024

An unprecedented chiral bisphosphine-catalyzed asymmetric Staudinger/aza-Wittig reaction of 2,2-disubstituted cyclohexane-1,3-diones is reported, enabling the facile access a broad range cis-3a-arylhydroindoles in high yields with excellent enantioselectivities. The key to success this work relies on first application bisphosphine DuanPhos reaction. effective reductive system has been established address challenging PV═O/PIII redox cycle associated catalyst. In addition, comprehensive experimental and computational investigations were carried out elucidate mechanism Leveraging newly developed chemistry, enantioselective total syntheses several crinine-type Amaryllidaceae alkaloids, including (+)-powelline, (+)-buphanamine, (+)-vittatine, (+)-crinane, have accomplished remarkable conciseness efficiency.

Language: Английский

Citations

7
A Fresh Twist on the Phospha-(Aza)-Wittig Reaction DOI
Chenyang Hu, Maren Pink, José M. Goicoechea

et al.

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

Published: March 30, 2025

The reactivity of an unsupported phosphinidene oxide, BnArNP═O (Bn = benzyl; Ar bulky aryl group), as the electrophilic partner in Wittig reactions with ylides is described. Reactions methylene-triphenylphosphorane (H2C═PPh3) and ethylidene-triphenyl-phosphorane (HMeC═PPh3), proceed expected, giving rise to phosphaalkene metathesis products triphenylphosphine oxide. This reaction can be extended other such N-(triphenylphosphoranylidene)methanamine (MeN═PPh3), afford aminoiminophosphane BnArNP═NMe. In these oxide plays role electrophile, which would typically remit organic carbonyl classical reactions. Further mechanistic insight into transformations gained by altering nature phosphorus-ylide. Upon reacting H2C═PMe3 (which possesses a smaller, more Lewis basic, phosphine) alternative product formed. transformation supports formation betaine intermediate that subsequently undergoes hydrogen-migration oxidized phosphorus(V) compound related phosphorus acid.

Language: Английский

Citations

0
Atroposelective Arene‐Forming Wittig Reaction by Phosphorus PIII/PV=O Redox Catalysis DOI Creative Commons

Kalipada Jana,

Zhengxing Zhao,

Janis Musies

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(37)

Published: June 28, 2024

Abstract The Wittig reaction is renowned as exceptionally versatile method for converting a diversity of aldehydes and ketones into alkenes. Recently, strategies chiral phosphine catalysis under P III /P V =O redox cycling emerged to render this venerable transformation stereoselective. Herein, we describe that enables the enantioselective synthesis pertinent biaryl atropisomers by means stereocontrolled arene‐forming reaction. Key process release an endogenous base from readily accessible tert ‐butyloxycarbonylated Morita–Baylis–Hillman adducts triggered catalyst intramolecularization, permitting mild atroposelective reactions. By strategy, broad obtained with up 94 : 6 enantioselectivity.

Language: Английский

Citations

3
Enantioselective Wittig Reactions Controlled by PIII/PV=O Redox Catalysis DOI Creative Commons
Christof Sparr,

Kalipada Jana

Synlett, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

Abstract The development of catalytic PIII/PV=O redox processes has transformed the Wittig reaction, traditionally plagued by stoichiometric phosphine oxide byproducts, into an efficient and more benign method for synthesizing alkenes. Recently, feasibility enantioselective catalysis was demonstrated using chiral catalysts, such as HypPhos. For example, atroposelective reaction Boc-MBH adducts, where endogenous base release facilitates ylide formation acid co-catalysis, allows enantiocontrol effective cycling, while catalyst-stereocontrolled reactions generally extend scope sustainability synthesis complex molecules. 1 Introduction 2 meso-Desymmetrizations 3 Atroposelective Catalysis 4 Conclusion

Language: Английский

Citations

0
Palladium-Catalyzed Asymmetric Larock Isoquinoline Synthesis to Access Axially Chiral 3,4-Disubstituted Isoquinolines DOI
Gang Wang,

Xinyu Tan,

Bing‐Xia Yan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(40), P. 27809 - 27818

Published: Sept. 26, 2024

Larock isoquinoline synthesis is one of the most efficient and straightforward approaches to construction 3,4-disubstituted isoquinolines. However, there have been no asymmetric versions for axially chiral isoquinolines since their initial report in 2001. Herein, we documented first example an by employing Pd(OAc)

Language: Английский

Citations

2
Chiral-Bisphosphine-Catalyzed Asymmetric Staudinger/Aza-Wittig Reaction: Development, Mechanism Study, and Synthetic Application DOI
Yefeng Tang, Hongzhi Yang,

Truc Quynh Nguyen

et al.

Synlett, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 22, 2024

Abstract The enantioselective desymmetrization of 2,2-disubstituted cyclohexane-1,3-diones has been realized through an unprecedented chiral-bisphosphine-catalyzed asymmetric Staudinger/aza-Wittig reaction. key to this work’s success lies in utilizing electronically rich and sterically hindered chiral bisphosphine reagent, namely DuanPhos, as a catalyst. In addition, unique reductive system was established address the requisite PIII/PV = O redox cycle. mechanism reaction elucidated combined computational experimental studies. Several crinine-type amaryllidaceae alkaloids have synthesized concisely, hinging on newly developed methodology.

Language: Английский

Citations

1
Trendbericht Organische Chemie 2024 DOI Open Access
Martin Breugst, Jennifer N. Andexer,

Lena Barra

et al.

Nachrichten aus der Chemie, Journal Year: 2024, Volume and Issue: 72(3), P. 44 - 67

Published: Feb. 29, 2024

Abstract Unter anderem das hat die Organik im letzten Jahr bewegt: milde Oxidation mit Elektrochemie, zu enantiomerenreinen Sulfonylverbindungen, Flüssigkristallphasen erkennen maschinellem Lernen, CO 2 reagiert Succinat und Carbamaten, eine Alternative Bisphenol A, Subporphyrine, photoschaltbare Spinmaterialien, photochemische Thiophen‐Ringerweiterung, Peptide werden Bor versehen cyclisiert. Die Zusammenstellung des Trendberichts koordiniert Martin Breugst, Universität Chemnitz.

Citations

0
Atroposelective Arene‐Forming Wittig Reaction by Phosphorus PIII/PV=O Redox Catalysis DOI Creative Commons
Christof Sparr,

Kalipada Jana,

Zhengxing Zhao

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(37)

Published: June 28, 2024

Abstract The Wittig reaction is renowned as exceptionally versatile method for converting a diversity of aldehydes and ketones into alkenes. Recently, strategies chiral phosphine catalysis under P III /P V =O redox cycling emerged to render this venerable transformation stereoselective. Herein, we describe that enables the enantioselective synthesis pertinent biaryl atropisomers by means stereocontrolled arene‐forming reaction. Key process release an endogenous base from readily accessible tert ‐butyloxycarbonylated Morita–Baylis–Hillman adducts triggered catalyst intramolecularization, permitting mild atroposelective reactions. By strategy, broad obtained with up 94 : 6 enantioselectivity.

Language: Английский

Citations

0
Recent advances in asymmetric P(III)/P(V) = O redox catalysis DOI
Changmin Xie,

Guzhou Chen,

Chen‐Guo Feng

et al.

Tetrahedron Letters, Journal Year: 2024, Volume and Issue: unknown, P. 155337 - 155337

Published: Oct. 1, 2024

Language: Английский

Citations

0