Iron carbonyl induced coupling of olefins to carbon monoxide

✍ Scribed by J. Mantzaris; E. Weissberger

• Publisher: Elsevier Science
• Year: 1972
• Tongue: French
• Weight: 233 KB
• Volume: 13
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)84943-1

✦ Synopsis

When neat diene I is treated with a 2:l molar ratio of Fe,(CO), or Fe(CO)S at 85O in a glass pressure bottle for 12 hours, coupling occurs through the b 2.3 double bond yielding ketone II. The product is stereochemically pure by TLC on silica gel, and nmr. (m/e)+ = 344 7Okmp = 271-272.5" While the analogous coupling of bicyclo[ 2.2.11 hepta-2,5-diene was observed1 as early as 1958, we find that iron carbonyl induced coupling of olefins to carbon monoxide is a general process and synthetically useful. Further, isolated double bonds are reactive, a 1.4 system being tnmecessary for reactivity. In the case of norbornadiene coupling, the ketonic product was assigned by nmr spectrocopy'to be the exo-trans-exo isomer. ---This assignment was confirmed by synthesis3 of all three cis-trans-cis isomers.