Synthesis and Stereoselective Reactions of New Stableα-Ferrocenyllithium Derivatives. An Umpolung of the Ferrocene Reactivity

Abstract

The reductive lithiation of various α-ferrocenylcarbinol derivatives yields stable α-ferrocenyllithium species (see scheme). These can be quenched with different electrophiles with complete retention of configuration.

Asymmetric Catalysis by Architectural and Functional Molecular Engineering: Practical Chemo- and Stereoselective Hydrogenation of Ketones

“…[83] This alcohol can be converted into a chiral ferrocenylphosphane with retention of configuration (Scheme 31). [143,83] …”

New Applications of Polyfunctional Organometallic Compounds in Organic Synthesis

“…[150] The mono- ferrocenyl compound 246 proves to be excellent for the asymmetric alkylation of allyl chlorides. [152] [144] REVIEWS P. Knochel et al Remarkable enantioselectivities were obtained in the reduction of a-acetamidoacrylates and 1,3-dicarbonyl compounds by using the Ferriphos ligands such as 244 [147,149] and the ligands 241 and 248.…”

Stereoselective Synthesis of Planar Chiral Ferrocenes

“…However, although the preparation a-ferrocenyllithiums from ortho-substituted aferrocenyl amines, ethers or sulfides 82 (X ¼ NMe 2 , OMe or SPh) requires lithium naphthalenide, this reaction proceeds without epimerization of 83 at low temperature (Scheme 2.19) to give products such as 84 [83]. This transformation represents an umpolung of the normal reactivity of a-ferrocenyl positions and increases the scope of products derived from 78.…”