Synthesis of tetrasubstituted 1-silyloxy-3-aminobutadienes and chemistry beyond Diels-Alder reactions.

Abstract:

:Electron-rich dienes have revolutionized the synthesis of complex compounds since the discovery of the legendary Diels-Alder cycloaddition reaction. This highly efficient bond-forming process has served as a fundamental strategy to assemble many structurally formidable molecules. Amino silyloxy butadienes are arguably the most reactive diene species that are isolable and bottleable. Since the pioneering discovery by Rawal, 1-amino-3-silyloxybutadienes have been found to undergo cycloaddition reactions with unparalleled mildness, leading to significant advances in both asymmetric catalysis and total synthesis of biologically active natural products. In sharp contrast, this class of highly electron-rich conjugated olefins has not been studied in non-cycloaddition reactions. Here we report a simple synthesis of tetrasubstituted 1-silyloxy-3-aminobutadienes, a complementarily substituted Rawal's diene. This family of molecules is found to undergo a series of intriguing chemical transformations orthogonal to cycloaddition reactions. Structurally diverse polysubstituted ring architectures are established in one step from these dienes.

journal_name

Nat Commun

journal_title

Nature communications

authors

Li X,Peng S,Li L,Huang Y

doi

10.1038/ncomms7913

subject

Has Abstract

pub_date

2015-04-21 00:00:00

pages

6913

issn

2041-1723

pii

ncomms7913

journal_volume

6

pub_type

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