Synthesis of vinyl bromides

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Organotrifluoroborates are rapidly and regioselectively converted into organic bromides in excellent yields under mild conditions, using sodium bromide in the presence of chloramine-T.
G. W. Kabalka, A. R. Mereddy, Organometallics, 2004, 23, 4519-4521.

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.

Reliable, operationally simple, catalytic α-selective hydroalumination reactions proceed in the presence of diisobutylaluminum hydride and (Ni(dppp)Cl₂), and, unlike uncatalyzed transformations, generate little or no alkynylaluminum byproducts. The derived α-vinyl halides and boronates can be synthesized through direct treatment with the appropriate electrophiles.
F. Gao, A. H. Hoveyda, J. Am. Chem. Soc., 2010, 132, 10961-10963.

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.

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.

(E)-β-Arylvinyl bromides were readily prepared in a short reaction time (1-2 min) by microwave irradiation of the corresponding 3-arylpropenoic acids in the presence of N-bromosuccinimide and a catalytic amount of lithium acetate.
C. Kuang, Q. Yang, H. Senboku, M. Tokuda, Synthesis, 2005, 1319-1325.

Using triethylamine as catalyst in Hunsdiecker reactions with N-halosuccinimides as Br⁺ or I⁺ source, cinnamic acids, and propiolic acids are converted to the corresponding α-halostyrenes and 1-halo-1-alkynes in good isolated yields within 1-5 min.
J. Prakash, S. Roy, J. Org. Chem., 2002, 67, 7861-7864.

Oxidative bromination of different types of olefins using Selectfluor/KBr afforded addition, monobromo-substituted, or Hunsdiecker-Borodin reaction products in good yields.
C. Ye, J. M. Shreeve, J. Org. Chem., 2004, 69, 8561-8563.

A chemoselective DBU-promoted elimination of vicinal dibromoalkanes having an adjacent O-functional group enables an efficient one-pot method for bromination-elimination of allyl alcohol derivatives to give 2-bromo allyl alcohol derivatives. Moreover, an efficient one-pot method for Sonogashira coupling was also achieved.
N. Kutsumura, K. Niwa, T. Saito, Org. Lett., 2010, 12, 3316-3319.

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.

A fast and convenient one-step procedure allows the conversion of α,β-unsaturated carbonyl compounds into their corresponding bromo-enones at room temperature under very mild conditions in high yields using NBS-Et₃N • 3 HBr in the presence of potassium carbonate in dichloromethane.
D. Jyothi, S. HariPrasad, Synlett, 2009, 2309-2311.

Aryl allylic alcohols are converted to halogenated unsaturated ketones or allylic halides under Moffatt-Swern Conditions using excess DMSO and oxalyl chloride or oxalyl bromide. Electron-poor aromatic rings favor formation of the halogenated ketone, while electron-donating substituents in the ortho or para positions favor formation of the allylic halide.
J. Yin, C. E. Gallis, J. D. Chisholm, J. Org. Chem., 2007, 72, 7054-7057.

α,β-Dihalopropanoate derivatives undergo efficient, selective dehydrohalogenation to form α-haloacrylate analogues in the presence of DMSO. A variety of α-halo Michael acceptors were prepared in dimethyl sulfoxide under mild, base-free conditions, including the preparation of α-bromoacrolein and α-chloro- and bromoacrylonitriles.
W. Li, J. Li, Z.-K. Wan, J. Wu, W. Massefski, Org. Lett., 2007, 9, 4607-4610.

C. Ye, J. M. Shreeve, J. Org. Chem., 2004, 69, 8561-8563.

Use of a zirconocene catalyst based on the Brintzinger ligand and catalytic amounts of methyl aluminoxanes (MAO) effect a >99% regiocontrol of Negishi carboaluminations of 1-alkynes in toluene.
B. H. Lipshutz, T. Butler, A. Lower, J. Am. Chem. Soc., 2006, 128, 15396-15398.

Unsaturated compounds such as alkenes, alkynes, allenes, and methylenecyclopropanes (MCPs) can be dibrominated within minutes by NBS and lithium bromide in THF at room temperature in good to excellent yields under mild conditions.
L.-X. Shao, M. Shi, Synlett, 2006, 1269-1271.

L.-X. Shao, M. Shi, Synlett, 2006, 1269-1271.

C-O bond cleavage of lithium alkoxides occurs readily at room temperature in the presence of titanium(IV) halides. Capture of the resultant carbocation by alkynes provides an efficient route to trisubstituted (E)-alkenyl halides with high stereoselectivity.
M.-L. Yao, T. R. Quick, Z. Wu, M. P. Quinn, G. W. Kabalka, Org. Lett., 2009, 11, 2647-2649.

α-Bromo- or α-chloro-α,β-unsaturated carbonyl compounds were prepared in good yields by addition of hydrobromic acid or hydrochloric acid to α,β-unsaturated carbonyl compounds in the presence of Oxone in CH₂Cl₂ followed by treatment of the resulting dihalides with Et₃N.
K.-M. Kim, I.-H. Park, Synthesis, 2004, 2641-2644.

Various bis-activated cyclopropenes undergo highly stereoselective ring-opening reactions to produce multisubstituted alkenyl halides in the presence of stoichiometric magnesium halides. Trapping of the magnesium enolate intermediates in situ allows the synthesis of highly functionalized compounds.
Y. Wang, H. W. Lam, J. Org. Chem., 2009, 74, 1353-1355.

A stereoselective multicomponent synthesis of (Z)-β-bromo Baylis-Hillman ketones uses MgBr₂ as both the Lewis acidic promoter and the bromine source for the Michael-type addition with α,β-acetylenic ketones to form an active β-bromo allenolate intermediate, which in turn attacks various aldehydes to afford β-bromo Baylis-Hillman adducts in good yields and Z-selectivity.
H.-X. Wei, R. L. Jasoni, J. Hu, G. Li, P. W. Pare, Tetrahedron, 2004, 60, 10233-10237.

A convenient and efficient method for aminobromination of alkylidenecyclopropanes is reported. This is exemplified in the stereoselective preparation of N-[(Z)-3-bromobut-3-en-1-yl]-p-toluenesulfonamides by using p-toluenesulfonamide and N-bromosuccinimide (NBS) as nitrogen and bromine sources, respectively.
X. Huang, W.-J. Fu, Synthesis, 2006, 1016-1017.

A new silver-catalyzed highly regio- and stereoselective difunctionalization reaction of simple terminal alkynes gives (Z)-β-haloenol acetate derivatives in good yields. The resulting products are versatile intermediates in organic synthesis.
Z. Chen, J. Li, H. Jiang, S. Zhu, Y. Li, C. Qi, Org. Lett., 2010, 12, 3262-3265.

Poly{[4-(hydroxy)(tosyloxy)iodo]styrene} was efficient in the halotosyloxylation reaction of alkynes with iodine or NBS or NCS. The polymer reagent could be regenerated and reused.
J.-M. Chen, X. Huang, Synthesis, 2004, 1557-1558.

A chemoselective isomerization of secondary-type propargylic alcohols under Appel-type reaction conditions in the presence of Ph₃P, CBr₄ and additives gives allenic bromides, propargylic bromides and brominated dienes.
N. Sakai, T. Maruyama, T. Konakahara, Synlett, 2009, 2105-2106.

Bromoboration of propyne with BBr₃ proceeds in syn-selectivity to produce (Z)-2-bromo-1-propenyldibromoborane, which is prone to stereoisomerization. Treatment with pinacol yields the stable and storable pinacolboronate. Negishi coupling gives trisubstituted (Z)-alkenylpinacolboronates in good yields. Iodinolysis of the boronates affords alkenyl iodides in good yields.
C. Wang, T. Tobrman, Z. Xu, E.-i. Negishi, Org. Lett., 2009, 11, 4092-4095.