Borrowing hydrogen: Indirect "Wittig" olerination for the formation of C-C bonds from alcohols

• Published in: European journal of organic chemistry Vol. 2006; no. 19; pp. 4367 - 4378
• Main Authors: Black, Phillip J., Edwards, Michael G., Williams, Jonathan M. J.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 25.09.2006
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; OXIDATION; CONVERSION; transfer hydrogenation; DOMINO-REACTIONS; iridium; SECONDARY ALCOHOLS; Wittig reactions; domino reactions; AMINES; CARBONYL; N-ALKYLATION; dehydrogenation; DERIVATIVES; METAL-COMPLEXES; CATALYTIC ELECTRONIC ACTIVATION
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.200600070

The successful development of an indirect three-step domino sequence for the formation of C-C bonds from alcohol substrates is described. An iridium-catalysed dehydrogenation of alcohol I affords the intermediate aldehyde 2. The desired C-C bond can then be formed by a facile Wittig olefination, yielding the intermediate alkene 3. In the final step the alkene is hydrogenated to afford the indirect Wittig product, the alkane 4. The key to this process is the concept of borrowing hydrogen; hydrogen removed in the initial dehydrogenation step is simply borrowed by the iridium catalyst. Functioning as a hydrogen reservoir, the catalyst facilitates C-C bond formation before subsequently returning the borrowed hydrogen in the final step. Herein we present full details of our examination into both the substrate and reaction scope and the limitations of the catalytic cycle. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).