Tandem Silylformylation−Crotylsilylation/Tamao Oxidation of Internal Alkynes: A Remarkable Example of Generating Complexity from Simplicity
- 13 November 2008
- journal article
- letter
- Published by American Chemical Society (ACS) in Organic Letters
- Vol. 10 (24) , 5593-5596
Abstract
The rhodium-catalyzed tandem silylformylation−crotylsilylation reaction has been extended to include internal alkynes. Tamao oxidation of the initial product leads to the production of a substituted enol, which undergoes highly diastereoselective tautomerization. The resulting one-pot procedure fashions three new stereocenters, a ketone, and a terminal alkene from a butenyl group, a propynyl group, a silyl hydride, H2O2, and CO.Keywords
This publication has 30 references indexed in Scilit:
- Studies on a Urea-Directed Stork−Crabtree Hydrogenation. Synthesis of the C1−C9 Subunit of (+)-ZincophorinThe Journal of Organic Chemistry, 2007
- Total Synthesis of Dolabelide DJournal of the American Chemical Society, 2006
- First Titanium-Catalyzed anti-1,4-Hydrosilylation of DienesOrganometallics, 2005
- Horner-Wadsworth-Emmons Reactions as a Facile Entry to Biogenetic Key SubstructuresSynlett, 2005
- Concerning the Synthesis of the Elusive anti,anti-Dipropionate Stereotriad via the Crotylation of β-Hydroxy α-Methyl Aldehydes with (Z)-Crotyltrifluorosilane. Application to the Synthesis of the C(7)−C(16) Segment of ZincophorinThe Journal of Organic Chemistry, 1998
- Synthesis of Stereopentad Subunits of Zincophorin and Rifamycin-S through Use of Chiral Allenyltin ReagentsThe Journal of Organic Chemistry, 1998
- Disilanyl Group as a Synthetic Equivalent of the Hydroxyl GroupSynlett, 1995
- Extremely Regioselective Intramolecular Silylformylation of AlkynesJournal of the American Chemical Society, 1995
- Rhodium-Catalyzed Intramolecular Silylformylation of Acetylenes: A Vehicle for Complete Regio- and Stereoselectivity in the Formylation of Acetylenic BondsJournal of the American Chemical Society, 1995
- Highly Regioselective and Stereoselective Silylformylation of Alkynes Under Mild Conditions Promoted by Dirhodium(II) PerfluorobutyrateOrganometallics, 1994