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Chiral organochlorosilanes derived from terpenes: diastereoselective hydrosilylation of methylene bicyclo[2.2.1]heptanes with HSiMenCln-2 (n=0-2)

Beckmann, Jens, Dakternieks, Dainis, Duthie, Andrew, Floate, Susan L., Foitzik, Richard C. and Schiesser, Carl H. 2004, Chiral organochlorosilanes derived from terpenes: diastereoselective hydrosilylation of methylene bicyclo[2.2.1]heptanes with HSiMenCln-2 (n=0-2), Journal of organometallic chemistry, vol. 689, no. 5, pp. 909-916, doi: 10.1016/j.jorganchem.2003.12.021.

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Title Chiral organochlorosilanes derived from terpenes: diastereoselective hydrosilylation of methylene bicyclo[2.2.1]heptanes with HSiMenCln-2 (n=0-2)
Formatted title Chiral organochlorosilanes derived from terpenes: diastereoselective hydrosilylation of methylene bicyclo[2.2.1]heptanes with HSiMenCln-2 (n=0-2)
Author(s) Beckmann, Jens
Dakternieks, Dainis
Duthie, Andrew
Floate, Susan L.
Foitzik, Richard C.
Schiesser, Carl H.
Journal name Journal of organometallic chemistry
Volume number 689
Issue number 5
Start page 909
End page 916
Publisher Elsevier BV
Place of publication Amsterdam, The Netherlands
Publication date 2004-03-01
ISSN 0022-328X
1872-8561
Keyword(s) hydrosilylation
hydroboration
terpenes
silanes
silicon
Summary The H2PtCl6 catalysed hydrosilylation of the terpenes (+)-α-fenchene (XI), (−)-2-methylene bornane (XII), (+)-camphene (XIII) and (−)-3-methylene fenchane (XIV) using HSiMe2Cl or HSiMeCl2 proceeds with high regioselectively and in some cases, with high diastereoselectivity. KF-assisted oxidation of the hydrosilylation products gives predominately endo-terpene alcohols. The alcohols have inverted endo/exo ratios to those formed by oxidative hydroboration. Reaction of XIV with HSiMe2Cl or HSiMeCl2 is accompanied by a clean rearrangement of the isocamphane skeleton into (+)-2-methylene bornane (XII) prior to hydrosilylation.

The hydrosilylation of α-fenchene, 2-methylene bornane, camphene and 3-methylene fenchane with chlorosilanes HSiMenCln − 2 (n=0–2) occurred with varying degrees of diastereoselectivity providing anti-Markovnikov product mixtures, in which the endo-isomers dominate over the exo-isomers. These mixtures were oxidized to give the corresponding terpene alcohols. 3-Methylene fenchane undergoes a rearrangement into 2-methylene bornane prior to hydrosilylation.

Language eng
DOI 10.1016/j.jorganchem.2003.12.021
Field of Research 039904 Organometallic Chemistry
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1 Refereed article in a scholarly journal
Copyright notice ©2004, Elsevier B.V.
Persistent URL http://hdl.handle.net/10536/DRO/DU:30002734

Document type: Journal Article
Collection: School of Biological and Chemical Sciences
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