A new approach to promoting sluggish Diels-Alder reactions: dihapto-coordination of the diene.
The cycloaddition between 1,3-cyclohexadiene and various enones and enals (methyl vinyl ketone, ethyl vinyl ketone, methacrolien) is accomplished at room temperature in yields ranging from 51 to 68% without the use of Lewis acids, high pressures, or microwave reactors. This normally sluggish cyclization is accomplished by precoordination of the diene to a pi-basic molybdenum complex. The eta2-bound metal is thought to promote a Michael reaction between the uncoordinated portion of the diene and the enone, and the resulting enolate then closes to form the cycloalkene product. The organic cycloadduct is removed by oxidation with air or with silver triflate in nearly quantitative yield. For more sterically hindered enones (e.g., mesityl oxide) and for methyl acrylate, the desired outcome requires the use of BF3.OEt2, and yields are significantly lower (15-35%)
Liu
Weijun
W
Department of Chemistry, University of Virginia, P.O. Box 400319, Charlottesville, Virginia, 22904-4319, USA.
You
Fei
F
Mocella
Christopher J
CJ
Harman
W Dean
WD
D000475:Alkenes / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis*; D003500:Cyclization; D003510:Cyclohexanes / Q000737:chemistry*; D053138:Cyclohexenes; D008982:Molybdenum / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D010422:Pentanones / Q000737:chemistry*
D000475:Alkenes; D001643:Bridged Bicyclo Compounds; D003510:Cyclohexanes; D053138:Cyclohexenes; D009942:Organometallic Compounds; D010422:Pentanones; C048401:1,4-cyclohexadiene; D008982:Molybdenum; C057461:1-pentene-3-one