Further Information
Literature
Related Reactions
Corey-Chaykovsky Reaction
Julia
Olefination
Peterson
Olefination
Schlosser Modification
Seyferth-Gilbert Homologation
Tebbe
Olefination
Wittig-Horner Reaction
Wittig Reaction
The Wittig Reaction allows the preparation of an alkene by the reaction of an aldehyde or ketone with the ylide generated from a phosphonium salt. The geometry of the resulting alkene depends on the reactivity of the ylide. If R is an electron withdrawing group, then the ylide is stabilized and is not as reactive as when R is alkyl. Stabilized ylides give predominantly (E)-alkenes whereas non-stabilized ylides lead to (Z)-alkenes (see also Wittig-Horner Reaction).
Mechanism of the Wittig Reaction
(2+2) Cycloaddition of the ylide to the carbonyl forms a four-membered cyclic intermediate, an oxaphosphetane. Preliminary posultated mechanisms lead first to a betaine as a zwitterionic intermediate, which would then close to the oxaphosphetane. The intermediacy of such betaines plays an important role in the Schlosser Modification. Betaines may be stabilized by lithium salts leading to side products; therefore, suitable bases in the Wittig Reaction are for example: NaH, NaOMe, NEt3.
The driving force is the formation of a very stable phosphine oxide:
Reactive ylides give rapid reaction and subsequent rapid ring opening to give the (Z)-alkene:
Recent Literature
Recycling the Waste: The Development of a Catalytic Wittig Reaction
C. J. O'Brien, J. L. Tellez, Z. S. Nixon, L. J. Kang, A. L. Carter, S. R. Kunkel,
K. C. Przeworski, G. A. Chass, Angew. Chem. Int. Ed., 2008, 48,
6836-6839.
PhCH=P(MeNCH2CH2)3N: A Novel Ylide for
Quantitative E Selectivity in the Wittig Reaction
Z. Wang, G. Zhang, I. Guzei, J. G. Verkade, J. Org. Chem., 2001, 66, 3521-3524.
Strong Bicyclic Guanidine Base-Promoted Wittig and Horner-Wadsworth-Emmons
Reactions
D. Simoni, M. Rossi, R. Rondanin, A. Mazzali, R. Baruchello, C. Malagutti, M.
Roberti, F. P. Ividiata,
Org. Lett., 2000, 2, 3765-3768.
Highly Tunable Stereoselective Olefination of Semistabilized
Triphenylphosphonium Ylides with N-Sulfonyl Imines
D.-J. Dong, H.-H. Li, S.-K. Tian, J. Am. Chem. Soc., 2010, 132, 5018-5020.
Potassium Hydride in Paraffin: A Useful Base for Organic Synthesis
D. F. Taber, C. G. Nelson, J. Org. Chem., 2006,
71, 8973-8974.
Generation of Phosphoranes Derived from Phosphites. A New Class of
Phosphorus Ylides Leading to High E Selectivity with Semi-stabilizing Groups in
Wittig Olefinations
V. K. Aggarwal, J. R. Fulton, C. G. Sheldon, J. de Vicente, J. Am. Chem. Soc., 2003, 125, 6034-6035.
One-Pot Synthesis of α,β-Unsaturated Esters, Ketones, and Nitriles from
Alcohols and Phosphonium Salts
W. Ding, J. Hu, H. Jin, X. Yu, S. Wang, Synthesis, 2018, 50,
107-118.
One-Pot, Tandem Wittig Hydrogenation: Formal C(sp3)-C(sp3)
Bond Formation with Extensive Scope
R. Devlin, D. J. Jones, G. P. McGlacken,
Org. Lett., 2020, 22, 5223-5228.
A Three-Step Route to a Tricyclic Steroid Precursor
D. F. Taber, R. B. Sheth, J. Org. Chem., 2008,
73, 8030-8032.
Chromatography-Free Wittig Reactions Using a Bifunctional Polymeric Reagent
P. S.-W. Leung, Y. Teng, P. H. Toy, Org. Lett., 2010,
12, 4996-4999.
Wittig Reactions in Water Media Employing Stabilized Ylides with Aldehydes.
Synthesis of α,β-Unsaturated Esters from Mixing Aldehydes, α-Bromoesters, and Ph3P
in Aqueous NaHCO3
A. El-Batta, C. Jiang, W. Zhao, R. Anness, A. L. Cooksy, M. Bergdahl, J. Org. Chem., 2007,
72, 5244-5259.
One-Pot Wittig Reactions in Water and in the Presence of a Surfactant
F. Orsini, G. Sello, T. Fumagalli, Synlett, 2006,
1717-1718.
Direct Conversion of N-Methoxy-N-methylamides (Weinreb Amides)
to Ketones via a Nonclassical Wittig Reaction
J. A. Murphy, A. G. J. Commeureuc, T. N. Snaddon, T. M. McGuire, T. A. Khan, K.
Hisler, M. L. Dewis, R. Carling, Org. Lett., 2005, 7, 1427-1429.
Reductive Halogenation Reactions: Selective Synthesis of Unsymmetrical
α-Haloketones
Z. Lao, H. Zhang, P. H. Toy,
Org. Lett., 2019, 21, 8149-8152.
PPh3O as an Activating Reagent for One-Pot Stereoselective
Syntheses of Di- and Polybrominated Esters from Simple Aldehydes
T.-Y. Hu, H. Wei, Y.-C. Luo, Y. Wang, Z.-Y. Wang, P.-F. Xu, J. Org. Chem.,
2016,
81, 2730-2736.
A highly stereoselective tandem Michael addition-Wittig reaction of
(3-carboxy-2-oxopropylidene)triphenylphosphorane and α,β-unsaturated aldehydes
gives multifunctional 6-carboxycyclohex-2-en-1-ones in excellent diastereo- and
enantioselectivities by employing the combined catalysis of a bulky chiral
secondary amine, LiClO4, and DABCO.
Y.-k. Liu, C. Ma, K. Jian, T.-Y. Liu, Y.-C. Chen, Org. Lett., 2009,
11, 2848-2851.
Wittig Olefination between Phosphine, Aldehyde, and Allylic Carbonate: A
General Method for Stereoselective Synthesis of Trisubstituted 1,3-Dienes with
Highly Variable Substituents
R. Zhou, C. Wang, H. Song, Z. He, Org. Lett., 2010,
12, 976-979.
In the presence of ruthenium-based olefin metathesis catalysts and
triphenylphosphine, α,β-unsaturated aldehydes can be olefinated with
diazoacetates. A tandem transformation of
terminal olefins to 1,3-dienoic olefins in a single operation based on olefin
cross-metathesis and Wittig olefination has been developed.
R. P. Murelli, M. L. Snapper, Org. Lett., 2007,
9, 1749-1752.
A Ba/Pd Catalytic System Enables Dehydrative Cross-Coupling and Excellent
E-Selective Wittig Reactions
P. Xie, W. Fu, X. Cai, Z. Sun, Y. Wu, S. Li, C. Gao, X. Yang, T.-P. Loh,
Org. Lett., 2019, 21, 7055-7059.
Tandem Wittig Reaction-Ring Contraction of Cyclobutanes: A Route to
Functionalized Cyclopropanecarbaldehydes
F. Cuccu, L. Serusi, A. Luridiana, F. Secci, P. Caboni, D. J. Aitken, A.
Frongia,
Org. Lett., 2019, 21, 7755-7758.
Synthesis of Vinyl Boronates from Aldehydes by a Practical Boron-Wittig
Reaction
J. R. Coombs, L. Zhang, J. P. Morken, Org. Lett.,
2015,
17, 1708-1711.
An Intramolecular Wittig Approach toward Heteroarenes: Synthesis of
Pyrazoles, Isoxazoles, and Chromenone-oximes
P. V. Khairnar, T.-H. Lung, Y.-J. Lin, C.-Y. Wu, S. R. Koppolu, A. Edukondalu,
P. Karanam, W. Lin,
Org. Lett., 2019, 21, 4219-4223.
Synthesis of Functionalized Furans via Chemoselective Reduction/Wittig
Reaction Using Catalytic Triethylamine and Phosphine
C.-J. Lee, T.-H. Chang, J. K. Yu, G. M. Reddy, M.-Y. Hsiao, W. Lin, Org. Lett.,
2016, 18, 3758-3761.
Transition-Metal-Free Synthesis of Trifluoromethylated Furans via a
Bu3P-Mediated Tandem Acylation-Wittig Reaction
M. Li, W. Zhou, Synlett, 2020,
31,
203-2038.
Synthesis of Polysubstituted Pyridines via a One-Pot Metal-Free Strategy
H. Wei, Y. Li, K. Xiao, B. Cheng, H. Wang, L. Hu, H. Zhai, Org. Lett.,
2015,
17, 5974-5977.
A Novel Synthesis of 4H-Chromen-4-ones via Intramolecular Wittig
Reaction
P. Kumar, M. S. Bodas,
Org. Lett., 2000, 2, 3821-3823.
Synthesis of Polysubstituted Isoquinolines and Related Fused Pyridines from
Alkenyl Boronic Esters via a Copper-Catalyzed Azidation/Aza-Wittig Condensation
Sequence
V. Jaryaram, T. Sridhar, G. V. M. Sharma, F. Berrée, B. Carboni, J. Org. Chem.,
2018, 83, 843-853.