Stereoselective synthesis cross-coupling reactions

Takeda Y, Shimizu M, Hiyama T. Straightforward synthesis of CFs-substituted triarylethenes by stereoselective threefold cross-coupling reactions. Angew. Chem. Lnt. Ed. 2007 46 8659-8661. 

Another very important aspect of these transition metal-catalysed cross-coupling reactions stems from the high selectivity observed with stereo-defined vinyl sulfides. Applications to the stereoselective syntheses of pheromones were straightforward (see [321] and references therein), as shown in the two-step synthesis of muscalure from (Z)-l-bromo-2-phenylthioethylene [322] involving its sequential coupling through the bromo and phenylthio substituents with the appropriate derivatives. 

The formation of (24) is >98% stereoselective. Efforts are currently being made to apply this methodology to the synthesis of carbacyclin (2S) A model study indicates that the Pd-catalyzed cross-coupling reaction of alkenylzinc derivatives is a promising method for the attachment of the so-called prostanoid (i>-side chain, as shown in equation (20). 

Cross-coupling reactions between 1-alkynyl halides and 1-alkenylboranes, which are readily available via hydroboration of alkynes, can also be catalyzed by Pd-phosphine complexes. Stereoselective synthesis of conjugated ( )-enynes 143 was achieved by the coupling of the alkynyl bromide with an alkenylborane [Eq. (48)] [69]. 

The nickel-catalyzed substitution of vinyl sulfides by Grignard reagents forms the basis of a procedure for the stereoselective synthesis of alkenes by sequential cross-coupling reactions developed by Naso and... 

Stereoselective radical reactions of carbonyl derivatives of heterocycles 00MI12. Suzuki-Miyaura cross-coupling reaction in organic synthesis (review contains many examples of reactions with participation of heterocycles) 02T9633. Tautomerism in diazoles, pyridines, and nucleic bases 02UK1120. 

Yanada R, Obika S, Oyama M, Takemoto Y (2004) Stereoselective synthesis of 3-aUtylide-neoxindoles using tandem in-mediated carbometalation and Pd-catalyzed cross-coupling reaction. Org Lett 6 2825-2828... 

Yanada R, Obika S, Kobayashi Y, Inokuma T, Oyama M, Yanada K, Taktanoto Y (2005) Stereoselective synthesis of 3-alkylideneoxindoles using tandcan indium-mediated carbmne-tallation and palladitmi-catalyzed cross-coupling reactions. Adv Synth Catal 347 1632-1642... 

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