Modern Lithium Carbenoid Chemistry (Chapter 11)

This chapter addresses the reactivity of a-lithiated organohalogens, ethers, and amines. Special emphasis is placed on their structure, configurational stability, and applications to synthetic chemistry in light of the recent advances that have appeared in the literature over the past decade. The chapter highlights the role played by aggregation and solvation on the structure-reactivity relationship. The characteristic features of a-lithiated halogens (Li/Hal) and a-lithiated ethers (Li/OR) carbenoids are discussed. These include: (i) the electrophilic reactivity, as observed in reactions with nucleophiles; (ii) the deshielding of the C atom in the NMR spectrum; and (iii) the C-X bond length in the corresponding solid state structures. The chapter concludes with a discussion on lithium-nitrogen carbenoids.