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

и другие.

JACS Au, Год журнала: 2024, Номер 4(9), С. 3358 - 3369

Опубликована: Авг. 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.

Язык: Английский

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

Ana Alvarez-Montoya,

Joseph P. Gillions,

Laura Winfrey

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 4856 - 4864

Опубликована: Март 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.

Язык: Английский

Процитировано

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

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(27)

Опубликована: Март 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.

Язык: Английский

Процитировано

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

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(6), С. 4244 - 4248

Опубликована: Фев. 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).

Язык: Английский

Процитировано

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

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(10), С. 8041 - 8049

Опубликована: Май 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.

Язык: Английский

Процитировано

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

Angewandte Chemie, Год журнала: 2024, Номер 136(27)

Опубликована: Март 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.

Процитировано

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

и другие.

JACS Au, Год журнала: 2024, Номер 4(9), С. 3358 - 3369

Опубликована: Авг. 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.

Язык: Английский

Процитировано

0