Synthesis of alkenyl halides

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β-Oxido phosphonium ylides, generated in situ from aldehydes and Wittig reagents react readily with electrophilic halogen sources to form predominantly or exclusively E-bromo- or iodosubstituted alkenes. The stereochemical outcome on halogenation is remarkably sensitive to alkylidene size [ethylidene(triphenyl)phosphorane is highly Z-selective].
D. M. Hodgson, T. Arif, J. Am. Chem. Soc., 2008, 130, 16500-16501.

(E)-β-Aryl vinyl halides are synthesized in good yield with excellent stereoselectivity and functional group tolerance from benzyl bromides. The convenient conditions involve a nucleophilic substitution with anions of CH₂I₂, ICH₂Cl, or CH₂Br₂ and a subsequent stereoselective base-induced elimination. A facile purification allows rapid access to a wide range of functionalized vinyl halides.
J. A. Bull, J. J. Mousseau, A. B. Charette, Org. Lett., 2008, 10, 5485-5488.

An efficient protocol for a highly stereoselective one-pot synthesis of (E)-β-aryl vinyl iodides and (E)-β-aryl vinyl bromides from styrenes is based on a ruthenium-catalyzed silylative coupling followed by a N-halosuccinimide-mediated halodesilylation reaction.
P. Pawluć, G. Hreczycho, J. Szudkowska, M. Kubicki, B. Marciniec, Org. Lett., 2009, 11, 3390-3393.

An optimized Julia olefination between readily available α-halomethyl sulfones and a variety of aldehydes afforded alkenyl halides in good to excellent yields with high E/Z stereoselectivities.
M.-E. Lebrun, P. Le Marquand, C. Berthelette, J. Org. Chem., 2006, 71, 2009-2013.

An efficient synthesis of α-iodo/bromo-α,β-unsaturated aldehydes/ketones directly from propargylic alcohols is catalyzed collaboratively by Ph₃PAuNTf₂ and MoO₂(acac)₂, and Ph₃PO as an additive helps suppress undesired enone/enal formation. Notable features of this method include low catalyst loadings, mild reaction conditions, and mostly good diastereoselectivity.
L. Ye, L. Zhang, Org. Lett., 2009, 11, 3646-3649.

Stoichiometric bromotrichloromethane in acetonitrile can replace solvent quantities of carbon tetrachloride in the synthesis of gem-dichloroalkenes from aldehydes in the presence of triphenylphosphine. Similarly, bromotrichloromethane in dichloromethane can be used for the Appel reaction of benzyl alcohols to form benzyl chlorides at r.t., which is commonly carried out in refluxing carbon tetrachloride.
S. G. Newman, C. S. Bryan, D. Perez, M. Lautens, Synthesis, 2011, 342-346.

Difluoromethyl 2-pyridyl sulfone acts as a novel and efficient gem-difluoroolefination reagent for both aldehydes and ketones. A fluorinated sulfinate intermediate in the reaction is relatively stable and can be observed by ¹⁹F NMR and trapped with CH₃I.
Y. Zhao, W. Huang, L. Zhu, J. Hu, Org. Lett., 2010, 12, 1444-1447.

Deprotonation of a 64:36 mixture of ethyl bromo(diphenylphosphono)acetate and ethyl dibromo(diphenylphosphono)acetate using NaH as base at 0 °C and subsequent reaction with various aldehydes provided unsaturated α-bromoesters in good yields and high E-selectivities.
T. Olpp, R. Brückner, Synthesis, 2004, 2135-2152.

The reaction of aromatic ketones with bis(trichloromethyl) carbonate afforded aryl-(Z)-vinyl chlorides in the presence of scandium triflate, DMF, and benzoyl chloride as catalysts. A plausible addition-elimination mechanism is proposed. This catalytic method enables a green route to aryl-(Z)-vinyl chlorides.
W. Su, C. Jin, Org. Lett., 2007, 9, 993-996.

(E)-β-Arylvinyl bromides were efficiently and stereoselectively prepared in high yields by microwave irradiation of the corresponding anti-3-aryl-2,3-dibromopropanoic acids in AcOH in the presence of AgOAc.
C. Kuang, H. Senboku, M. Tokuda, Tetrahedron, 2005, 61, 637-642.

(Z)-1-Bromo-1-alkenes were stereoselectively efficiently prepared in high yields by microwave irradiation of the corresponding anti-2,3-dibromoalkanoic acids in DMF using Et₃N as base. Microwave-assisted one-pot syntheses of terminal alkynes and enynes from 2,3-dibromoalkanoic acids were also developed.
C. Kuang, Q. Yang, H. Senboku, M. Tokuda, Tetrahedron, 2005, 61, 4043-4052.

Application of (PhO)₃P-halogen-based reagents allows the preparation of vinyl halides in good to excellent yields from enolizable ketones, whereas aldehydes afforded the corresponding gem-dihalides. The halogenation proceeded smoothly under mild conditions.
A. Spaggiari, D. Vaccari, P. Davoli, G. Torre, F. Prati, J. Org. Chem., 2007, 72, 2216-2219.