68364-22-7Relevant academic research and scientific papers
A NEW PRACTICAL SYNTHESIS OF SILYL ENOL ETHERS. PART.I. FROM SIMPLE ALDEHYDES AND KETONES.
Cazeau, P.,Duboudin, F.,Moulines, F.,Babot, O.,Dunogues, J.
, p. 2075 - 2088 (2007/10/02)
A new, practical route to enoxysilanes is described from simple enolizable aldehydes or ketones, using the trimethylchlorosilane-sodium iodide-tertiary amine reagent in acetonitrile.From certain aldehydes, an onium intermediate has been isolated.A conformational study of this onium intermediate and a thermal unimolecular syn-elimination process may explain the stereoselectivity of the reaction.Such an interpretation can be extended to all the aldehydes and ketones considered.Steric factors related to the nature both of the cabonyl derivative and of the amine play a capital role for the regio- as well as for the stereo-control of the reaction.
Stereospecific Synthesis of Metalated Alkoxymethyl Vinyl Ethers
McGarvey, Glenn J.,Bajwa, Joginder S.
, p. 4091 - 4092 (2007/10/02)
The thermolysis of substituted bicyclohept-5-enes provides expedient access to stannylated vinyl ethers of defined stereochemistry.Alkoxymethyl substitution on the vinyl oxygen is found to significantly improve the hydrolytic stability of several substituted vinyl ethers.
Synthesis of Precursors of C4 and C5 Cumulenones
Brown, Roger F. C.,Coulston, Karen J.,Eastwood, Frank W.,Gatehouse, Bryan M.,Guddatt, Luke W.,et al.
, p. 2509 - 2524 (2007/10/02)
Bicyclohept-5-en-2-one was condensed with 2,2-dimethyl-1,3-dioxan-4,6-dione in the presence of titanium tetrachloride/pyridine to yield 5-(bicyclohept-5'-en-2'-ylidene)-2,2-dimethyl-1,3-dioxan-4,6-dione (6a) which on pyrolysis at 520-560 deg/0.01 mm gave acetone, carbon dioxide, cyclopentadiene and butatrienone.In the same way 5-(7'-oxabicyclohept-5'-en-2'-ylidene)-2,2-dimethyl-1,3-dioxan-4,6-dione (6b) was prepared from 7-oxabicyclohept-5-en-2-one and on pyrolysis at 570 deg/0.01 mm it gave acetone, carbon dioxide, furan and butatrienone.Alkylation of 2-trimethylsiloxybicyclohepta-2,5-diene with phenylthiomethyl chloride with titanium tetrachloride as catalyst followed by condensation with 2,2-dimethyl-1,3-dioxan-4,6-dione gave an endo/exo mixture of 5-(3'-phenylthiomethylbicyclohept-5'-en-2'-ylidene)-2,2-dimethyl-1,3-dioxan-4,6-dione.The structure of the endo isomer was established by X-ray crystallography.Oxidation of the phenylthiomethyl compound with m-chloroperbenzoic acid yielded the sulfoxide which was converted by boiling in carbon tetrachloride into 5-(3'-methylenebicyclohept-5'-en-2'-ylidene)-2,2-dimethyl-1,3-dioxan-4,6-dione (8).Preliminary studies on the fragmentation of compound (8) have shown that at 450 deg/0.01 mm it is converted into acetone, carbon dioxide and products showing ketene absorption at 2140 cm-1.The formation of pentatetraenone has not been established with certainty.The 3'-phenylsulfonylmethyl, phenylselenyl and methyl derivatives of (6a) are also described.
A serendipitous, high yield conversion of norbornenone to tricyclo2,7>octan-4-one
Ragauskas, Arthur J.,Stothers, J.B.
, p. 2254 - 2256 (2007/10/02)
Simmons-Smith cyclopropanation of the trimethylsilyl enol ether of norbornenone has been found to generate the 2-trimethylsilyl ether of homoquadricyclene, homoketonization of which affords the symmetrical tricyclo2,7>octan-4-one regiospecifically with high stereoselectivity favoring inversion of configuration.
