Categories: C=C Bond Formation >
Synthesis of (E)-alkenes
Name Reactions
Schlosser Modification of the Wittig Reaction
Recent Literature
The efficient olefination from organozinc reagents with aldehydes is
exploited in a new synthesis of aryl and alkyl olefins.
J.-X. Wang, Y. Fu, Y. Hu, K. Wang, Synthesis, 2003, 1506-1510.
Aryl tosylhydrazones react with t-BuOK, ClFeTPP, (MeO)3P,
and aldehydes to furnish olefins with high E selectivity through a
Wittig-type pathway via the corresponding diazo compounds, metal carbenes
and phosphorous ylides. A Horner-Wadsworth-Emmons-type reaction of ethyl
diazoacetate with aldehydes occurs with high E selectivity in the
presence of LiBr via the phosphonate anion, formed through an Arbuzov
reaction under completely base-free conditions.
V. K. Aggarwal, J. R. Fulton, C. G. Sheldon, J. de Vicente, J. Am. Chem. Soc., 2003, 125, 6034-6035.
An efficient and facile copper(II) acetylacetonate catalyzed synthesis of
functionalized bis(arylmethyl)zinc reagents from arylmethyl halides followed by
olefination with aromatic aldehydes gives (E)-stilbenes in good yields.
Aluminum trichloride was found to be the key ingredient in these reactions.
Y. Fu, X. Hu, Y. Chen, Y. Yang, H. Hou, Y. Hu, Synthesis, 2012, 44,
1030-1036.
A Ni-catalyzed acceptorless dehydrogenative coupling of alcohols with nitriles
followed by decyanation provides diversely substituted olefins with formation of
formamide as a sole byproduct. The significant advantages of this unprecedented
C=C bond-forming methodology are the low-cost nickel catalyst, good functional
group compatibility, convenience, high reaction selectivity and efficiency.
S. P. Midya, M. Subaramanian, R. Babu, V. Yadav, E. Balaraman, J. Org. Chem., 2021, 86,
7552-7562.
An aza-Peterson olefination of N-phenyl imines or ketones with allyl- or
benzyltrimethylsilane provides 1,3-dienes and stilbene derivatives in high
yields. Silanes can be deprotonated using Schlosser's base.
T. K. Britten A. J. Basson, D. D. Roberts, M. G. McLaughlin, Synthesis, 2021, 53,
3535-3544.
N-sulfonyl imines undergo olefination reactions with various
benzylidenetriphenylphosphoranes or allylidenetriphenylphosphoranes under mild
reaction conditions to afford an array of both Z- and E-isomers of
conjugated alkenes in good to excellent yields and with greater than 99:1
stereoselectivity depending on the N-sulfonyl group.
D.-J. Dong, H.-H. Li, S.-K. Tian, J. Am. Chem. Soc., 2010,
132, 5018-5020.
D.-J. Dong, H.-H. Li, S.-K. Tian, J. Am. Chem. Soc., 2010,
132, 5018-5020.
A modification of the classical Julia-Lythgoe olefination using
sulfoxides instead of sulfones affords 1,2-di-, tri-, and tetrasubstituted
olefins in moderate to excellent yields and E/Z selectivity. The mild
conditions involve in situ benzoylation and SmI2/HMPA-mediated reductive elimination
as key steps.
J. Pospisil, T. Pospisil, I. E. Marko, Org. Lett., 2005, 7, 2373-2376.
A stereoselective synthesis of tetrasubstituted alkenylboronates, which are
useful synthetic intermediates for further functionalizations, was established
via the lithiation/nucleophilic addition reaction of 1,1-organodiboronates to
carbonyl compounds.
K. Endo, M. Hirokami, T. Shibata, J. Org. Chem., 2010,
75, 3469-3472.
A versatile and operationally simple base-catalyzed multi-component domino
reaction between α,β-unsaturated carbonyl compounds, aldehydes, and alcohols is
described, providing a new efficient, and stereoselective one-pot preparation of
trisubstituted alkenes and 1,3-dienes.
H. Habib-Zahmani, S. Hacini, C. Bories, J. Rodriguez, Synthesis, 2005,
2151-2156.
Fe(0) is cost-effective, environmentally friendly alternative to Cr(II) for
the olefination of carbonyls by activated polyhalides. Fe(0) proved
compatible with a wide range of functionality, such as unprotected phenol,
aryl nitro, carboxylic acid, and alkyl nitrile.
J. R. Falck, R. Bejot, D. K. Barma, A. Bandyopadhyay, S. Joseph, C.
Mioskowski, J. Org. Chem., 2006, 71, 8178-8182.
Thiouronium ylides are valuable olefination reagents for stereodivergent
carbonyl olefinations. Using these reagents, aldehydes are converted to Z-alkenes
with high stereoselectivity and broad substrate scope, while N-tosylimines
provide a similarly proficient entry to E-alkenes. In-depth computational
and experimental studies clarified the mechanistic details of this unusual
reactivity.
J. Merad, P. S. Grant, T. Stopka, J. Sabbatani, R. Meyrelles, A. Preinfalk,
J. Matyasovsky, B. Maryasin, L. González, N. Maulide, J. Am. Chem. Soc.,
2022, 144, 12536-12543.
A domino oxidation of primary alcohols gives α,β-unsaturated compounds using the
combination of PCC-NaOAc and stabilized Wittig reagents.
J. Shet, V. Desai, S. Tilve, Synthesis,
2004,
1859-1863.
A series of vinyl sulfonamides was synthesized using the Horner reaction of
aldehydes and diphenylphosphorylmethanesulfonamide. The sulfonamide reagent was
easily prepared and can be stored indefinitely.
D. C. Reuter, J. E. McIntosh, A. C. Guinn, A. M. Madera, Synthesis, 2003, 2321-2324.