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Jeganmohan M, Shanmugasundaram M, Cheng CH: Highly regio- and chemoselective palladium-catalyzed propargylallylation of activated olefins: a novel route to 1,7-enyne derivatives. J Org Chem. 2004 Jun 11;69(12):4053-62.
An efficient method for the synthesis of 1,7-enyne derivatives via phosphine-palladium-catalyzed three-component assembling of activated olefins, allylic chlorides, and allenylstannanes is described. Substituted arylethylidene malononitriles 1a-g (RCH=C (CN)(2): R = C (6) H (5) (1a), p-ClC (6) H (4) (1b), p-OMeC (6) H (4) (1c), p-NO (2) C (6) H (4) (1d), 1-naphthyl (1e), 2-furyl (1f), and 2-thienyl (1g)) undergo propargylallylation with allylic chlorides 2a-e (allyl chloride (2a), methallyl chloride (2b), 4-chloropent-2-ene (2c), cinnamyl chloride (2d), and 3-chlorocyclohexene (2e)) and n-tributylallenylstannane (n-Bu (3) SnCH=C=CH (2), 3a) in the presence of Pd (PPh (3))(4) in toluene to afford the corresponding 1,7-enyne derivatives 4a-m in good to excellent yields. The catalytic reaction is highly regioselective, with the propargyl group adding to the carbon where the R group is attached and the allyl group adding to the carbon connected to the CN groups of activated olefins 1a-g. The present catalytic reaction is successfully extended to substituted arylethylidene-1,3-indanediones 5a-j (RCH = (1,3-indanedione): R = C (6) H (5) (5a), p-ClC (6) H (4) (5b), p-BrC (6) H (4) (5c), p-OMeC (6) H (4) (5d), p-NO (2) C (6) H (4) (5e), p-CNC (6) H (4) (5f), p-biphenyl (5g), 1-naphthyl (5h), 2-thienyl (5i), and 2-benzo [b] furane-2-yl (5j)) and substituted 2,2-dimethyl-5-(arylethylidene)-1,3-dioxane-4,6-diones 7a,b (RCH = (1,3-dioxane-4,6-dione): R = p-NO (2) C (6) H (4) (7a), p-OMeC (6) H (4) (7b)). The three-component assembling of these substrates with allylic chlorides (2a,b,d,e) and n-tributylallenylstannane (n-Bu (3) SnCH=C=CH (2), 3a) proceeds smoothly to afford the corresponding 1,7-enyne derivatives 6a-m and 8a-d in good to excellent yields. The catalytic propargylallylation can be further applied to the activated dienes, C (6) H (5) CH=CH=CR (2) (R (2) = (CN)(2) (9a), 1,3-indanedione (9b), 2,2-dimethyl-1,3-dioxane-4,6-dione (9c)), with allylic chlorides (2a,b,d) and allenylstannane 3a to give regio- and chemoselective 1,2-addition products 10a-h in good to excellent yields. A plausible mechanism based on an eta (1)-allenyl eta (3)-allyl palladium intermediate is proposed to account for the catalytic three-component reaction. |
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