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8.1.23 Product Subclass 23: γ-Lithio Ethers and Related Compounds

DOI: 10.1055/sos-SD-008-00512

Caine, D.Science of Synthesis, (20068775.

General Introduction

The reaction of an electron-donor molecule (a nucleophile) with an electron-acceptor molecule (an electrophile) is the most widely used method for the formation of CC bonds in organic synthesis, and organolithium compounds are among the most important electron-donor species available. Frequently, an efficient method for the synthesis of complex molecules involves the utilization of a three-carbon, or larger donor species, which contains a functional group at the γ-position (a d3-synthon) as one of the partners in a key step.[‌1‌] For this reason much effort is directed toward the syntheses of lithium reagents (LiCCCX) containing neutral ether and related functional groups at the γ-position; indeed, such reagents containing a γ-1-ethoxyethoxy substituent [X=OCH(OEt)Me] are among the first and most widely used reagents of this type. Likewise, γ-hydroxylated compounds (X=OH), which can be converted into the corresponding lithium γ-alkoxides (X=OLi) prior to the formation of the organolithium reagents, are also widely used. The versatility of this methodology is widened still further by the utilization of γ-sulfanyl (X=SR1) and γ-amino (X=NR1R2) organolithium reagents as electron donors in organic synthesis.

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