Best Synthetic Methods Carbon-Carbon Bond Formation.doc

Best Synthetic Methods: Carbon-Carbon Bond Formation Carbon-carbon bond construction is the basis for all of organic chemistry. Important methods for the construction of single, double, and triple bonds have been described. While ketones can be prepared by the addition of organometallic reagents to amides or to nitriles, they are often prepared by the addition of the organometallic reagent to an aldehyde such as 1. In a subsequent step, the product secondary alcohol is oxidized to the ketone. William J. Kerr of the University of Strathclyde has now found Org. Lett. 2006, 8, 5073. DOI: 10.1021/ol061903l that if the intermediate alkoxide is worked up with the Mukaiyama reagent 2, the ketone 3 is formed directly. The alkoxides derived from the addition of Grignard reagents can be converted to the ketones, but yields are better with the alkoxides derived from organolithium reagents. Skipped diynes such as 6 are often prepared as precursors to the skipped Z-dienes that are ubiquitous in fatty acids. Sebastian Wendeborn of Syngenta Crop Protection in Basel has developed Org. Lett. 2006, 8, 5629. DOI: 10.1021/ol0623769 a new route to such skipped diynes, based on the coupling of an alkynylalane 4 with a propargylic methanesulfonate. The regioisomeric allenic products are apparently not formed. The aldol condensation of esters with aldehydes has required the formation of the stoichiometric ester enolate. Don M. Coltart of Duke University has now shown Org. Lett. 2006, 8, 1503. DOI: 10.1021/ol060413q that Hunig’s base in the presence of MgBr2 etherate is sufficient to induce the condensation of a thioester such as 7 with the aldehyde 1. Note that the product thioester 8 could easily be reduced to the aldehyde or homologated to the ketone. In a continuation of his work on innovative and practical procedures for acylation, Yoo Tanabe of Kwansei Gakuin University, Hyogo, has described Org. Lett. 2006, 8, 5215. DOI: 10.1021/ol0619361 the activation of a carboxylic ac