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8.1.21 Product Subclass 21: α-Lithioamines

DOI: 10.1055/sos-SD-008-00412

Gawley, R. E.; O'Connor, S.; Klein, R.Science of Synthesis, (20068677.

General Introduction

This section covers sp3-hybridized organolithium compounds having a nitrogen on the carbanionic carbon. Therefore, sp2-hybridized organolithium compounds such as lithiated enamines and heterocycles, as well as α-aminoenolates are excluded from this section. The product subclass is divided into six sections: (1) tertiary amines that are metalated at the α-carbon, but with no other stabilizing functionality and are called unstabilized; (2) carbanions that are adjacent to a dipole induced by a nitrogen substituent such as a nitroso, amide, or amidine group; (3) carbanions that are mesomerically stabilized by virtue of being allylic or benzylic; (4) carbanions that are both dipole and mesomerically stabilized; (5) dipole-stabilized carbanions that have an additional heteroatom on the metal-bearing carbon, and (6) species whose nitrogens have a formal positive charge, and upon deprotonation give an ylide. The rationale for this subdivision is based on general trends in the dynamic and chemical properties of organolithiums. Among the properties that can vary are the method of synthesis (considering the kinetic barrier to deprotonation in some cases), configurational stability, reactivity toward various electrophiles (including other metals), propensity toward reactions such as cyclizations, cycloadditions, and sigmatropic rearrangements, and the susceptibility to single-electron transfer.

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