165277-06-5Relevant articles and documents
Structure and reactivity of an isolable seven-membered-ring trans-alkene
Hurlocker, Brisa,Hu, Chunhua,Woerpel
, p. 4295 - 4298 (2015)
The isolation and characterization of a trans-oxasilacycloheptene is reported. Single-crystal X-ray crystallographic studies indicate a high level of strain and deviation from ideal geometry. Reactions with several electrophiles demonstrated the nucleophilicity of the C=C double bond, affording oxasilacycloheptane and tetrahydrofuran products as single diastereomers.
Diastereoselective synthesis of seven-membered-ring trans-alkenes from dienes and aldehydes by silylene transfer
Greene, Margaret A.,Prevost, Michel,Tolopilo, Joshua,Woerpel
supporting information; experimental part, p. 12482 - 12484 (2012/09/05)
Silver-catalyzed silylene transfer to alkenes forms vinylsilacyclopropanes regioselectively. These allylic silanes undergo additions to aldehydes to form seven-membered-ring trans-alkenes with high diastereoselectivity. The high reactivity of the trans-alkenes is evidenced by their formal [1,3]-sigmatropic rearrangement reactions and the rapid additions of oxygen-hydrogen bonds across the carbon-carbon double bonds.
Preparation and Reactions of Diorganozincs from Dienic Silyl Enol Ethers
Devasagayaraj, A.,Schwink, L.,Knochel, P.
, p. 3311 - 3317 (2007/10/02)
The hydroboration of the dienic silyl enol ethers 1a-d with Et2BH produces organoboranes which are readily converted under mild conditions by a treatment with Et2Zn to the corresponding dialkylzincs 2a-d.These organometallics react after transmetallation with CuCN*2LiCl with various electrophiles affording polyfunctional silyl enol ethers of type 4.In the presence of the chiral catalyst (1R,2R)-bis(trifluoromethanesulfonamido)cyclohexane 6, the dialkylzinc 2b was added to various aldehydes leading to hydroxy silyl enol ethers of type 8 in satisfactory yields (45-77percent) and excellent enantioselectivities (85 to >96percent ee).The chiral products 8 can be oxidatively cyclized using t-BuOOH and catalytic amounts of VO(acac)2 furnishing trisubstituted tetrahydopyrans like 9a,b with high diastereoselectivity.An iodoalkoxylation of 8a affords after HI elimination and Jones oxidation the unsaturated valerolactone 13.
