The Corey-Seebach Reagent in the 21st Century: A Review

Abstract

The Corey-Seebach reagent plays an important role in organic synthesis because of its broad synthetic applications. The Corey-Seebach reagent is formed by the reaction of an aldehyde or a ketone with 1,3-propane-dithiol under acidic conditions, followed by deprotonation with n-butyllithium. A large variety of natural products (alkaloids, terpenoids, and polyketides) can be accessed successfully by utilizing this reagent. This review article focuses on the recent contributions (post-2006) of the Corey-Seebach reagent towards the total synthesis of natural products such as alkaloids (lycoplanine A, diterpenoid alkaloids, etc.), terpenoids (bisnorditerpene, totarol, etc.), polyketide (ambruticin J, biakamides, etc.), and heterocycles such as rodocaine and substituted pyridines, as well and their applications towards important organic synthesis.

Chemoselective Heterogeneous Hydrogenation of Sulfur Containing Quinolines under Mild Conditions

“…Finally, we wanted to demonstrate the utility of the sulfur functionalities by providing some downstream product modifications (Scheme ). Dithianes can be seen as protecting groups for carbonyl compounds and can be used for Corey–Seebach-type umpolung reactions . Since carbonyls are often labile under hydrogenation conditions (see 2q ), the tolerance of dithianes offers new possibilities to retain carbonyl moieties under a hydrogen atmosphere and offers the chance to do further umpolung reactions to obtain more complex structures.…”

“…Dithianes can be seen as protecting groups for carbonyl compounds and can be used for Corey− Seebach-type umpolung reactions. 38 Since carbonyls are often labile under hydrogenation conditions (see 2q), the tolerance of dithianes offers new possibilities to retain carbonyl moieties under a hydrogen atmosphere and offers the chance to do further umpolung reactions to obtain more complex structures. By adding n-BuLi to 2s and subsequently 2-furoyl chloride, THQ 4 was successfully obtained in moderate yield due to a competing reaction with the nitrogen (Scheme 2A).…”

Sulfur in Waste‐Free Sustainable Synthesis: Advancing Carbon–Carbon Coupling Techniques

“…The α-position of alkyl sulfides is traditionally considered to be chemically active. Its reactivity is associated with the generation of stabilized intermediates: carbanions (for example, the Corey-Seebach reaction [36] ) or radicals (Giesetype reactions [37,38] ). In both cases, the reactions cannot be classified as waste-free since either an equivalent amount of a very strong base (BuLi, for example) or a radical initiator (( t BuO) 2, for example) is required, respectively.…”