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. Attached Files Name Description MIMEType Size Downloads 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 Collections: Faculty of Science, Engineering and Built Environment School of Biological and Chemical Sciences Related Links Link Description Connect to published version (restricted access) Go to link with your DU access privileges     Unless expressly stated otherwise, the copyright for items in DRO is owned by the author, with all rights reserved. Versions Version Filter Type Thu, 23 Oct 2008, 09:58:07 EST Wed, 03 Jun 2009, 10:26:46 EST Mon, 13 Jan 2014, 14:51:10 EST Fri, 13 Jun 2014, 22:42:33 EST Fri, 17 Oct 2014, 08:16:54 EST Filtered Full Citation counts:   Cited 7 times in TR Web of Science Cited 10 times in Scopus Search Google Scholar Access Statistics: 779 Abstract Views, 1 File Downloads  -  Detailed Statistics Created: Mon, 07 Jul 2008, 08:33:01 EST