Hydride Shuttle Catalysis: From Conventional to Inverse Mode DOI Creative Commons
Iakovos Saridakis, Immo Klose, Benjamin T. Jones

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(9), P. 3358 - 3369

Published: Aug. 19, 2024

Hydride shuttle catalysis has emerged as a powerful synthetic platform, enabling the selective formation of C–C bonds to yield sp3-rich structures. By virtue compelling reactivity sterically encumbered Lewis acids from frustrated pair regime, hydride enables regioselective functionalization alkyl amines at either α- or β-position. In contrast classical acid reactivity, increased steric hindrance prevents interaction with basic amine itself, instead leading reversible abstraction α-carbon. The created positive charge facilitates occurrence transformations before rebound similar capture event happen. this Perspective, we outline broad selection featuring catalysis, well recently developed approach inverse catalysis. Both strategies give rise wide array functionalized and offer elegant approaches otherwise elusive bond formations.

Language: Английский

B(C6F5)3-Catalyzed Dehydrogenation of Pyrrolidines to Form Pyrroles DOI Creative Commons

Ana Alvarez-Montoya,

Joseph P. Gillions,

Laura Winfrey

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4856 - 4864

Published: March 18, 2024

Pyrroles are important N-heterocycles found in medicines and materials. The formation of pyrroles from widely accessible pyrrolidines is a potentially attractive strategy but an underdeveloped approach due to the sensitivity oxidative conditions required achieve such transformation. Herein, we report catalytic that employs commercially available B(C6F5)3 operationally simple procedure allows serve as direct synthons for pyrroles. Mechanistic studies have revealed insights into borane-catalyzed dehydrogenative processes.

Language: Английский

Citations

9
Lewis Acid‐Driven Inverse Hydride Shuttle Catalysis DOI Creative Commons
Benjamin T. Jones, Nuno Maulide

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: March 29, 2024

Abstract Inverse hydride shuttle catalysis provides a multicomponent platform for the highly efficient synthesis of alkaloid frameworks with exquisite diastereoselectivity. However, number limitations hinder this method, primarily strict requirement electron‐deficient acceptors. Herein, we present general Lewis acid‐driven approach to address constraint, and have developed two broad strategies enabling modular complex azabicycles that were entirely unattainable using previous method. The enhanced synthetic flexibility facilitates streamlined asymmetric cyclization, leading concise total (−)‐tashiromine.

Language: Английский

Citations

4
Accessing Highly Substituted Indoles via B(C6F5)3-Catalyzed Secondary Alkyl Group Transfer DOI Creative Commons

Salma A. Elsherbeni,

Rebecca L. Melen, Alexander P. Pulis

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 4244 - 4248

Published: Feb. 23, 2024

Herein, we report a synthetic method to access range of highly substituted indoles via the B(C6F5)3-catalyzed transfer 2° alkyl groups from amines. The transition-metal-free catalytic approach has been demonstrated across broad and amine donors, including various substituents on both reacting components, useful C(3)-alkylated indole products. process can be performed using Schlenk line techniques in combination with commercially available B(C6F5)3·nH2O solvents, which obviates requirement for specialized equipment (e.g., glovebox).

Language: Английский

Citations

3
B(C6F5)3-Catalyzed C(sp3)–H Alkylation of Tertiary Amines with Electron-Deficient Olefins: Determinants of Site Selectivity DOI

Xin-Yue Zhou,

Yingbo Shao,

Ruiting Guo

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 8041 - 8049

Published: May 8, 2024

The reason for the site selectivity previously reported B(C6F5)3-catalyzed C(sp3)–H alkylation of tertiary amines with electron-deficient olefins remains a mystery. appears to be governed by number electron-withdrawing groups (EWGs) on olefin: one EWG results in α-alkylation, whereas two EWGs (one each end double bond) result β-alkylation. In this study, we solved mystery and unlocked pathway β-alkylation bearing only EWG. Control experiments density functional theory calculations provided detailed picture reaction mechanism both α- Furthermore, demonstrated broad scope reaction.

Language: Английский

Citations

3
Lewis Säure‐Getriebene Inverse Hydrid‐Shuttle Katalyse DOI Creative Commons
Benjamin T. Jones, Nuno Maulide

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(27)

Published: March 29, 2024

Abstract Inverse Hydrid‐Shuttle Katalyse bildet eine Plattform für die hocheffiziente und diastereoselektive Synthese von Alkaloidstrukturen durch Multikomponentenreaktionen. Mehrere Einschränkungen hindern jedoch breite Anwendbarkeit dieses Ansatzes, darunter vor allem Notwendigkeit nach besonders elektronenarmen Akzeptoren. Hier präsentieren wir einen allgemeinen, Lewis Säuren getriebenen Ansatz, um diese Einschränkung anzugehen, haben zwei Strategien entwickelt, modulare komplexer azabicyclischer Systeme ermöglichen, mit der früheren Methode unerreichbar waren. Die so gewonnene synthetische Flexibilität führt zu einer verbesserten asymmetrischen Cyclisierung, kurze Totalsynthese des Alkaloids (−)‐Tashiromin ermöglicht hat.

Citations

0
Hydride Shuttle Catalysis: From Conventional to Inverse Mode DOI Creative Commons
Iakovos Saridakis, Immo Klose, Benjamin T. Jones

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(9), P. 3358 - 3369

Published: Aug. 19, 2024

Hydride shuttle catalysis has emerged as a powerful synthetic platform, enabling the selective formation of C–C bonds to yield sp3-rich structures. By virtue compelling reactivity sterically encumbered Lewis acids from frustrated pair regime, hydride enables regioselective functionalization alkyl amines at either α- or β-position. In contrast classical acid reactivity, increased steric hindrance prevents interaction with basic amine itself, instead leading reversible abstraction α-carbon. The created positive charge facilitates occurrence transformations before rebound similar capture event happen. this Perspective, we outline broad selection featuring catalysis, well recently developed approach inverse catalysis. Both strategies give rise wide array functionalized and offer elegant approaches otherwise elusive bond formations.

Language: Английский

Citations

0