Dimethyl Acetylene Dicarboxylate

Introduction

Dimethyl acetylene dicarboxylate (DMAD) is an electron-deficient alkyne diester widely used as dienophile and dipolarophile in cycloaddition reactions. It is used as a standard in Diels-Alder reactions to check the efficiency of various dienes. It can undergo [2+2] cycloaddition ­reactions, [1] 1,3-dipolar cycloaddition with 1,3-dipoles, for example azides, [2] diazoalkanes, nitrile oxide, carbonyl ylides, [3] and azomethine ylides. Besides it is also a powerful Michael acceptor and can accept various nucleophiles, for example nitrogen, oxygen, carbon, sulfur, and phosphorus.

DMAD is inexpensively available, and it can be prepared from maleic acid via a bromination-dehydrohalogenation sequence to furnish acetylene dicarboxylic acid, [4] which, upon esterification with methanol using sulfuric acid, gives dimethyl acetylene dicarboxylate. [5]

Scheme 1

References

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