A strategy for the controllable generation of organic superbases from benchtop-stable salts

Abstract

Organic superbases are a distinct class of strong base that enable numerous modern reaction applications. Despite their great synthetic potential, widespread use and study of superbases are limited by their air sensitivity and difficult preparation. To address this, we report air-stable carboxylate salts of BTPP and P2-t-Bu phosphazene superbases that, when added to solution with an epoxide, spontaneously generate freebase. These systems function as effective precatalysts and stoichiometric prereagents for superbase-promoted addition, substitution and polymerization reactions. In addition to improving the synthesis, shelf stability, handling and recycling of phosphazenes, this approach enables precise regulation of the rate of base generation in situ. The activation strategy effectively mimics manual slow addition techniques, allowing for control over a reaction's rate or induction period and improvement of reactions that require strong base but are also sensitive to its presence, such as Pd-catalyzed coupling reactions.

Graphical abstract: A strategy for the controllable generation of organic superbases from benchtop-stable salts

Supplementary files

Article information

Article type
Edge Article
Submitted
16 Apr 2024
Accepted
07 May 2024
First published
29 May 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024, Advance Article

A strategy for the controllable generation of organic superbases from benchtop-stable salts

S. J. Sujansky, G. A. Hoteling and J. S. Bandar, Chem. Sci., 2024, Advance Article , DOI: 10.1039/D4SC02524E

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