Synthesis of vinyl chlorides

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A commercial nanogold catalyst enables a highly regioselective hydrochlorination of unactivated alkynes using a novel chlorinating reagent with a high concentration of HCl without overchlorination or hydration. The reaction tolerates various functional groups and can be conducted under open air.
S. Liang, R. Ebule, G. B. Hammond, B. Xu, Org. Lett., 2017, 19, 4524-4527.

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.

The use of copper tubings enables a simple continuous flow synthesis of alkenyl chlorides in very good yields from the corresponding readily available alkenyl iodides with full retention of the double bond geometry. The reaction time was reduced 24 to 48fold compared to the batch process.
A. Nitelet, V. Kairouz, H. Lebel, A. B. Charette, G. Evano, Synthesis, 2019, 51, 251-257.

The use of catalytic amounts of copper iodide and trans-N,N′-dimethylcyclohexane-1,2-diamine in the presence of tetramethylammonium chloride or bromide enables the transformation of easily accessible alkenyl iodides into their far less available chlorinated and brominated derivatives in excellent yields and with full retention of the double bond geometry.
A. Nitelet, G. Evano, Org. Lett., 2016, 18, 1904-1907.

A mild and metal-free method for the chlorodeboronation of organotrifluoroborates using trichloroisocyanuric acid (TCICA) converts aryl-, heteroaryl-, alkenyl-, alkynyl-, and alkyltrifluoroborates into the corresponding chlorinated products in good yields. This method tolerates a broad range of functional groups.
G. A. Molander, L. N. Cavalcanti, J. Org. Chem., 2011, 76, 7195-7203.

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.

A facile Pd-catalyzed conversion of aryl and vinyl triflates allows convenient access to various aryl, heteroaryl, and vinyl halides in good to excellent yields and with greatly simplified conditions relative to our previous report.
J. Pan, X. Wang, Y. Zhang, S. L. Buchwald, Org. Lett., 2011, 13, 4974-4976.

The use of easy to handle DMPU/HX (X = Br or Cl) reagents enables an atom-economical and metal-free method for the regio- and stereo-selective hydrohalogenation of ynones and ynamides under mild conditions. The reaction tolerates a wide range of functional groups.
X. Zeng, Z. Lu, S. Liu, G. B. Hammond, B. Xu, J. Org. Chem., 2017, 82, 13179-13187.

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.

PhICl₂ in wet DMF forms an efficient system for difunctionalization of various alkenes to provide either regioselective chloroformyloxylated products or α-chlorinated olefinic products, depending on the type of structure of the original unsaturated starting material. The mechanism of the reaction is proposed and discussed.
L. Liu, D. Zhang-Negrerie, Y. Du, K. Zhao, Org. Lett., 2014, 16, 436-439.

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.

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.

In a method for the Friedel-Crafts-type insertion reaction of acetylene with acid chlorides in chloroaluminate ionic liquids, the use of ionic liquids not only serves to avoid the use of carbon tetrachloride or 1,2-dichloroethane but also suppresses side reactions, and enables a simpler purification procedure, giving a range of aromatic and aliphatic β-chlorovinyl ketones in high yield and purity.
D. J. M. Snelders, P. J. Dyson, Org. Lett., 2011, 13, 4048-4051.

Iridium complexes show high catalytic activity in regio- and stereoselective intermolecular additions of acid chlorides to terminal alkynes to afford valuable (Z)-β-chloro-α,β-unsaturated ketones. Whereas a N-heterocyclic carbene (NHC) is an efficient ligand for the addition of aroyl chlorides, dicyclohexyl(2-methylphenyl)phosphine (PCy₂(o-Tol)) enables the reaction of aliphatic acid chlorides.
T. Miura, T. Biyajima, T. Fujii, M. Murakami, J. Am. Chem. Soc., 2012, 134, 194-196.

2-Alkynyl esters are stereo- and regioselectively converted to E-β-chloro-α-iodo-α,β-unsaturated esters by exposure to Bu₄NI in refluxing dichloroethane. Single-isomer tetrasubstituted olefins bearing four different carbon substituents are then synthesized by sequential palladium-catalyzed coupling reactions.
A. B. Lemay, K. S. Vulic, W. W. Ogilvie, J. Org. Chem., 2006, 71, 3615-3618.

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.

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 metal-free regio- and stereoselective method provides (E)-configured α-halo enamides, vinyl thioethers, and vinyl ethers using aqueous HX (X = F, Cl, Br, I). The method offers high functional group compatibility and regio- and stereoselectivity, mild conditions, high efficiency, and rapid transformation. Additionally, methods for the (E)- to (Z)-isomerization are described.
W. Cao, P. Chen, L. Wang, H. Wen, Y. Liu, W. Wang, Y. Tang, Org. Lett., 2018, 20, 4507-4511.

Halosulfonylation of terminal alkynes was achieved with sulfonylhydrazides as the sulfonyl precursor and inexpensive iron halide as halide source in the presence of TBHP to yield (E)-β-chloro and bromo vinylsulfones regio- and stereoselectively.
X. Li, X. Shi, M. Fang, X. Xu, J. Org. Chem., 2013, 78, 9499-9504.

A practical, convenient, and highly regioselective copper-catalyzed 1,4-chlorotrifluoromethylation of 1,3-enynes affords chloro- and CF₃-containing tetrasubstituted allene derivatives with very good yield. A 1,4-bromotrifluoromethylation is also reported.
J. Huang, Y. Jia, X. Li, J. Duan, Z.-X. Jiang, Z. Yang, Org. Lett., 2021, 23, 2314-2319.

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Previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of a catalyst that is generated in situ and used with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents.
M. J. Koh, T. T. Ngyuen, H. Zhang, R. R. Schrock, A. H. Hoveyda, Nature, 2016, 531, 459-465.

The use of bisphosphine ligands with a large P-Pd-P bite angle allowed to synthesize Z-chlorinated internal alkenes in good yields by a selective Suzuki-Miyaura monocoupling process of 9-alkyl-9-BBN with 1,1-dichloro-1-alkenes. These monochlorinated olefins could be further transformed providing stereospecifically trisubstituted olefins.
F. Liron, C. Fosse, A. Pernolet, E. Roulland, J. Org. Chem., 2007, 72, 2220-2223.