Evolution of Dithiane-Based Strategies for the Construction of Architecturally Complex Natural Products

TLDR

Umpolung-based strategies, especially 1,3‑dithiane linchpins acting as acyl anion equivalents, have become widely used since the late 1970s for assembling complex natural products due to their synthetic accessibility and reactivity. This account reviews the evolution of dithiane chemistry in our laboratory.

Abstract

Umpolung-based strategies play a significant role in organic synthesis. Particularly important are 1,3-dithiane linchpins, which serve as convenient acyl anion equivalents. The general synthetic accessibility and impressive reactivity of 1,3-dithianes have thus led to widespread application. Since the late 1970s, dithianes have featured prominently in our program directed toward the synthesis of complex natural and unnatural products, both for effective union of advanced fragments and for multicomponent linchpin couplings. In this Account, we present the evolution of dithiane chemistry in our laboratory.