Hydrovinylation Explained

In organic chemistry, hydrovinylation is the formal insertion of an alkene into the C-H bond of ethylene :

The more general reaction, hydroalkenylation, is the formal insertion of an alkene into the C-H bond of any terminal alkene. The reaction is catalyzed by metal complexes. A representative reaction is the conversion of styrene and ethylene to 3-phenybutene:^[1]

$\backslash ce\; +\; \backslash longrightarrow\; \backslash ce$

Ethylene dimerization

The dimerization of ethylene gives 1-butene is another example of a hydrovinylation. In the Dimersol and Alphabutol Processes, alkenes are dimerized for the production of gasoline and for comonomers such as 1-butene. These processes operate at several refineries across the world at the scales of about 400,000 tons/year (2006 report).^[2] 1-Butene is amenable to isomerization to 2-butenes, which is used in Olefin conversion technology to give propylene.

In organic synthesis

The addition can be done highly regio- and stereoselectively, although the choices of metal, ligands, and counterions often play very important role. Many metals have also been demonstrated to form active catalysts, including nickel^{[3] [4] [5]} and cobalt.^{[6] [7] [8]}

In a stoichiometric version of a hydrovinylation reaction, nucleophiles add to an electrophilic transition metal alkene complex, forming a C-C bond. The resulting metal alkyl undergoes beta-hydride elimination, liberating the vinylated product.^[9]

Hydroarylation

Hydroarylation is again a special case of hydrovinylation. Hydroarylation has been demonstrated for alkyne and alkene substrates. An early example was provided by the Murai reaction, which involves the insertion of alkenes into a C-H bond of acetophenone. The keto group directs the regiochemistry, stabilizing an aryl intermediate.^[10]

When catalyzed by palladium carboxylates, a key step is electrophilic aromatic substitution to give a Pd(II) aryl intermediate.^[11] Gold behaves similarly.^[12] Hydropyridination is a similar reaction, but entails addition of a pyridyl-H bond to alkenes and alkynes.^[13]

See also

• Vinylation, the process of affixing a vinyl group

References

1. Encyclopedia: Comprehensive Organic Synthesis II (Second Edition). Hydrovinylation Reactions in Organic Synthesis. T. V. RajanBabu . G. A. Cox . 10.1016/B978-0-08-097742-3.00533-4. 2014. 1582–1620. 5. 5.32 Hydrovinylation Reactions in Organic Synthesis. 978-0-08-097743-0.
2. Olefin Metathesis: The Early Days (Nobel Lecture). Yves Chauvin. 2006. 10.1002/anie.200601234. 16724296. Angew. Chem. Int. Ed.. 45. 23. 3740–3747. Yves Chauvin.
3. Ho, C.-Y. . He, L. . 2010 . 9182–9186 . Catalytic Intermolecular Tail-to-Tail Hydroalkenylation of Styrenes with alpha-Olefins: Regioselective Migratory Insertion Controlled by a Nickel/N-Heterocyclic Carbene . 48 . 20853303 . Angew. Chem. Int. Ed. . 49 . 10.1002/anie.201001849 .
4. Ho, C.-Y. . He, L. . 2012 . 1481–1483 . Shuffle Off the Classic Beta-Si Elimination by Ni-NHC Cooperation: Implication for C–C Forming Reactions Involving Ni-Alkyl-Beta-Silanes . 10 . 22116100 . Chem. Commun. . 48 . 10.1039/c1cc14593b .
5. 10.15227/orgsyn.085.0248 . (R)-3-Methyl-3-Phenyl-1-Pentene Via Catalytic Asymmetric Hydrovinylation . Organic Syntheses . 2008 . 85 . 19672483 . Smith . C. R. . Zhang . A. . Mans . D. J. . Rajanbabu . T. V. . 248–266 . 2723857 .
6. Grutters, M. M. P. . Muller, C. . Vogt, D. . 2006 . 7414–5 . Highly Selective Cobalt-Catalyzed Hydrovinylation of Styrene . 23 . 16756275. J. Am. Chem. Soc. . 128 . 10.1021/ja058095y .
7. Hilt, G. . Danz, M. . Treutwein, J. . 2009 . 3322–5 . Cobalt-Catalyzed 1,4-Hydrovinylation of Styrenes and 1-Aryl-1,3-butadienes . 15 . 19583205 . Org. Lett. . 11 . 10.1021/ol901064p .
8. Sharma, R. K. . RajanBabu, T. V. . 2010 . 3295–7 . Asymmetric Hydrovinylation of Unactivated Linear 1,3-Dienes . 10 . 20163120. J. Am. Chem. Soc. . 2836389 . 132 . 10.1021/ja1004703 .
9. 10.15227/orgsyn.066.0095. Vinylation of Enolates with a Vinyl Cation Equivalent: trans-3-Methyl-2-Vinylcyclohexanone . Organic Syntheses . 1988 . 66 . 95. Tony C. T. Chang, Myron Rosenblum, Nancy Simms .
10. Murai. Shinji. Kakiuchi. Fumitoshi. Sekine. Shinya. Tanaka. Yasuo. Kamatani. Asayuki. Sonoda. Motohiro. Chatani. Naoto. 1993-12-09. Efficient catalytic addition of aromatic carbon-hydrogen bonds to olefins. Nature. en. 366. 6455. 529–531. 10.1038/366529a0. 1993Natur.366..529M. 5627826.
11. Jia, C. . Kitamura, T. . Fujiwara, Y. . Catalytic Functionalization of Arenes and Alkanes Via C-H Bond Activation. Acc. Chem. Res.. 2001. 34. 8. 633–639. 10.1021/ar000209h. 11513570.
12. 10.1016/j.tet.2008.01.081. Recent advances in syntheses of heterocycles and carbocycles via homogeneous gold catalysis. Part 1: Heteroatom addition and hydroarylation reactions of alkynes, allenes, and alkenes. 2008. Shen. Hong C.. Tetrahedron. 64. 18. 3885–3903.
13. 10.1021/acs.organomet.5b01021. Chromium-Catalyzed Regioselective Hydropyridination of Styrenes. 2016. Li. Yuexuan. Deng. Gongda. Zeng. Xiaoming. Organometallics. 35. 5. 747–750.