A simple synthesis of 1-(1,3-butadienyl) carbonates and carbamates

✍ Scribed by Paul F. De Cusati; R.A. Olofson

• Book ID: 104222085
• Publisher: Elsevier Science
• Year: 1990
• Tongue: French
• Weight: 293 KB
• Volume: 31
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)88817-6

✦ Synopsis

Crotonaldehyde and its congeners are conveniently and often stereospecifically converted to trans-1 -(l ,Sbutadienyl) carbonates and carbamates by treatment first with potassium terf-butoxide and then with a chloroformate or carbamyl chloride. In 1975, Oppolzer' reported the synthesis of tfans-N-(1 ,Sbutadienyl) carbamates 1 by treatment of imines from crotonaldehyde with either MeS(O)CH*-Na+ in DMSO or (Me.$i),N-Na+ in toluene at ca. -50 "C followed by acylation with chloroformates. Both Oppolze$ and Overman3 have shown the utility of 1 as a Diels-Alder diene in the regio-and stereospecific total syntheses of several alkaloids and Oppolzer' has patented 1 as a monomer in the production of fibers and films. Despite the value of 1 in synthetic and polymer chemistry, the analogous Obutadienyl carbamates 2 and carbonates 3 of a&unsaturated aldehydes were unknown prior to this work.4 This also is surprising