Wittig & Horner-Emmons Reaction

Wittig and Horner-Emmons reactions are useful reactions which react with aldehydes and ketones to form carbon-carbon double bonds and are frequently utilized in organic syntheses.1)
Recently, syntheses of α,β-unsaturated esters have increasingly been performed using Wittig and Horner-Emmons reagents. In Horner-Emmons reactions, carbon-carbon double bonds generally lead to the E-form. Attempts to selectively obtain Z-form are being investigated and reaction solvents, temperatures, and new Horner-Emmons reagents are being examined.2)

Ando has developed ethyl (diaryl) phosphonoacetate and found a method for the synthesis of selective Z-α,β-unsaturated ester.3) This method has received much attention as it utilizes quaternary ammonium hydroxide. The reaction is stable toward water and does not require special reactive technique. The reaction has an exceedingly high selectivity for Z-α,β-unsaturated ester.

Wittig Reaction

Horner-Emmons Reaction

Wittig Reaction

D2164 D2164 N0700 N0700 D2907 D2907
C1759 C1759 H1240 H1240 T1510 T1510
T1498 T1498 N0701 N0701 A1439 A1439
B1206 B1206 C1009 C1009 C1739 C1739
F0331 F0331 M0828 M0828 T2001 T2001
T1958 T1958 T2565 T2565 D1655 D1655
D2056 D2056 T1458 T1458 T2002 T2002
D1654 D1654 B1208 B1208 C1061 C1061
E0421 E0421 A1305 A1305 A1007 A1007
A1012 A1012 A0862 A0862 B2025 B2025
B0824 B0824 B0970 B0970 C1286 C1286
C1378 C1378 E0407 E0407 T1944 T1944
C1641 C1641 E0382 E0382 E0549 E0549
H0545 H0545 H0540 H0540 I0552 I0552
M1326 M1326 T1363 T1363 M0779 M0779
M0253 M0253 P1182 P1182 T1506 T1506
P1438 P1438 P1200 P1200 T1644 T1644
D2164 (1,3-Dioxolan-2-yl)methyltriphenylphosphonium Bromide
N0700 (1-Naphthylmethyl)triphenylphosphonium Chloride
D2907 (2,4-Dichlorobenzyl)triphenylphosphonium Chloride
C1759 (2-Chlorobenzyl)triphenylphosphonium Chloride
H1240 (2-Hydroxybenzyl)triphenylphosphonium Bromide
T1510 (2-Trimethylsilylethyl)triphenylphosphonium Iodide
T1498 (3-Trimethylsilyl-2-propynyl)triphenylphosphonium Bromide
N0701 (4-Nitrobenzyl)triphenylphosphonium Bromide
A1439 (Acetylmethylene)triphenylphosphorane
B1206 (Bromomethyl)triphenylphosphonium Bromide
C1009 (Chloromethyl)triphenylphosphonium Chloride
C1739 (Cyanomethyl)triphenylphosphonium Chloride
F0331 (Formylmethyl)triphenylphosphonium Chloride
M0828 (Methoxymethyl)triphenylphosphonium Chloride
T2001 (Triphenylphosphoranylidene)acetaldehyde
T1958 (Triphenylphosphoranylidene)acetonitrile
T2565 (Triphenylphosphoranylidene)ketene
D1655 2-(1,3-Dioxan-2-yl)ethyltriphenylphosphonium Bromide
D2056 2-(1,3-Dioxolan-2-yl)ethyltriphenylphosphonium Bromide
T1458 2-(Trimethylsilyl)ethoxymethyltriphenylphosphonium Chloride
T2002 2-(Triphenylphosphoranylidene)acetophenone
D1654 2-Dimethylaminoethyltriphenylphosphonium Bromide
B1208 3-Bromopropyltriphenylphosphonium Bromide
C1061 4-(Carboxybutyl)triphenylphosphonium Bromide
E0421 4-Ethoxybenzyltriphenylphosphonium Bromide
A1305 Acetonyltriphenylphosphonium Chloride
A1007 Allyltriphenylphosphonium Bromide
A1012 Allyltriphenylphosphonium Chloride
A0862 Amyltriphenylphosphonium Bromide
B2025 Benzyltriphenylphosphonium Bromide
B0824 Benzyltriphenylphosphonium Chloride
B0970 Butyltriphenylphosphonium Bromide
C1286 Cinnamyltriphenylphosphonium Bromide
C1378 Cyclopropyltriphenylphosphonium Bromide
E0407 Ethoxycarbonylmethyl(triphenyl)phosphonium Bromide
T1944 Ethyl (Triphenylphosphoranylidene)acetate
C1641 Ethyl 2-(Triphenylphosphoranylidene)propionate
E0382 Ethyltriphenylphosphonium Bromide
E0549 Ethyltriphenylphosphonium Iodide
H0545 Heptyltriphenylphosphonium Bromide
H0540 Hexyltriphenylphosphonium Bromide
I0552 Isopropyltriphenylphosphonium Iodide
M1326 Methoxycarbonylmethyl(triphenyl)phosphonium Bromide
T1363 Methyl (Triphenylphosphoranylidene)acetate
M0779 Methyltriphenylphosphonium Bromide
M0253 Methyltriphenylphosphonium Iodide
P1182 Phenacyltriphenylphosphonium Bromide
T2718 Tributyl(1,3-dioxolan-2-ylmethyl)phosphonium Bromide
T1506 Triphenyl(tetradecyl)phosphonium Bromide
P1438 Triphenylpropargylphosphonium Bromide
P1200 Triphenylpropylphosphonium Bromide
T1644 Triphenylvinylphosphonium Bromide
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Horner-Emmons Reaction

B1923 B1923 B1714 B1714 C1595 C1595
D3688 D3688 D3689 D3689 D3336 D3336
D3813 D3813 D3873 D3873 M1208 M1208
D3708 D3708 P1193 P1193 P1258 P1258
D2423 D2423 B1781 B1781 B1795 B1795
C1430 C1430 H0779 H0779 O0208 O0208
D3709 D3709 D3875 D3875 D2548 D2548
D2547 D2547 M1210 M1210 D2873 D2873
D2445 D2445 T1582 T1582 F0340 F0340
T2135 T2135 D1524 D1524 D1523 D1523
P1265 P1265
B1923 4,4'-Bis(diethylphosphonomethyl)biphenyl
B1714 Bis(2,2,2-trifluoroethyl) (Methoxycarbonylmethyl)phosphonate
C1595 Diethyl (3-Chlorobenzyl)phosphonate
D3688 Diethyl (4-Bromobenzyl)phosphonate
D3689 Diethyl (4-Iodobenzyl)phosphonate
D3336 Diethyl (4-Methylbenzyl)phosphonate
D3813 Diethyl (Hydroxymethyl)phosphonate
D3873 Diethyl (Methoxymethyl)phosphonate
M1208 Diethyl (Methylthiomethyl)phosphonate
D3708 Diethyl (N-Methoxy-N-methylcarbamoylmethyl)phosphonate
P1193 Diethyl (Phthalimidomethyl)phosphonate
P1258 Diethyl 1-Pyrrolidinemethylphosphonate
D2423 Diethyl 2,2-Diethoxyethylphosphonate
B1781 Diethyl 2-Bromoethylphosphonate
B1795 Diethyl Benzylphosphonate
C1430 Diethyl Cyanomethylphosphonate
H0779 Dimethyl (2-Hydroxyethyl)phosphonate
O0208 Dimethyl (2-Oxopropyl)phosphonate
D3709 Diphenyl (N-Methoxy-N-methylcarbamoylmethyl)phosphonate
D3875 Diphenyl 4-Bromo-alpha-chlorobenzylphosphonate
D2548 Ethyl Di-o-tolylphosphonoacetate [Horner-Emmons Reagent]
D2547 Ethyl Diphenylphosphonoacetate [Horner-Emmons Reagent]
M1210 Methoxymethyl(diphenyl)phosphine Oxide
D2873 Methyl Diethylphosphonoacetate
D2445 Methyl(diphenyl)phosphine Oxide
T1582 Tetraethyl p-Xylylenediphosphonate
F0340 Triethyl 2-Fluoro-2-phosphonoacetate
T2135 Triethyl 2-Phosphonopropionate
D1524 Triethyl 3-Phosphonopropionate
D1523 Triethyl Phosphonoacetate
P1265 Trimethyl Phosphonoacetate
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Literature

1) H.-J. Altenbach, Angew. Chem. Int. Ed., 1979, 18, 940 [DOI]; R. D. Little, G. W. Muller, J. Am. Chem. Soc., 1981, 103, 2744 [DOI]; C. Schmidt, N. H. Chishti, T. Breining, Synthesis, 1982, 391.
2) S. K. Thompson, C. H. Heathcock, J. Org. Chem., 1990, 55, 3386 [DOI]; A. Redjal, J. Seyden-Penne, Tetrahedron Lett., 1974, 1733 [DOI].
3) W. C. Still, C. Gennari, Tetrahedron Lett., 1983, 24, 4405 [DOI].
4) K. Ando, Tetrahedron Lett., 1995, 36, 4105 [DOI]; K. Ando, J. Org. Chem., 1997, 62, 1934 [DOI]; K. Ando, Yuki Gosei Kagaku Kyokaishi (J. Synth. Org. Chem., Jpn.), 2000, 58, 869; K. Ando, T. Oishi, M. Hirama, H. Ohno, T. Ibuka, J. Org. Chem., 2000, 65, 4745 [DOI]; Tokyo Ksei Kogyo, Jpn. Kokai Tokkyo Koho 10 265486, 1998.

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