1,2-Dichloroethylene1

(E)

[156-60-5]  · C2H2Cl2  · 1,2-Dichloroethylene  · (MW 96.94) (Z)

[156-59-2]

(useful reagent for the synthesis of chloroenynes, enediynes, chlorodienes, conjugated trienes, and tetraenes)

Physical Data: mp -80.5 °C (Z), -50 °C (E); bp 60.3 °C (Z), 48.4 °C (E); d 1.284 g cm-3 (Z), 1.257 g cm-3 (E).

Solubility: insol water; sol alcohol, ether, and most other organic solvents.

Form Supplied in: colorless liquid; widely available. Drying: before use, (E)- or (Z)-1,2-dichloroethylene must be distilled under an inert atmosphere.

Handling, Storage, and Precautions: (E)- or (Z)-1,2-dichloroethylene has a slightly acrid odor; it is gradually decomposed by air, light, and moisture, forming HCl; it must be stored in a refrigerator. Exposure to vapor may produce nausea and weakness. Use in a fume hood.

Derived Organolithium Reagents.

(E)-1,2-Dichloroethylene can be metalated with n-Butyllithium at -110 °C to give, after carboxylation, (E)-2,3-dichloroacrylic acid (eq 1).2 With (Z)-1,2-dichloroethylene the reaction leads to lithium chloroacetylide, which can be trapped with an appropriate electrophile (eq 2).3,4

Acetylene Equivalent.

Reaction of (E)-1,2-dichloroethylene with enones leads to dichlorocyclobutanes and, after reduction, to cyclobutenes (eq 3).5

Coupling Reactions.

When treated with nucleophilic agents such as sodium arenethiolate,6 sodium acetate,7 or lithium diphenylphosphide,8 (Z)- or (E)-1,2-dichloroethylene lead to disubstituted products (eq 4).

The nickel- or palladium-catalyzed coupling reaction between organometallics and (Z)- or (E)-1,2-dichloroethylene9,10 allows for the preparation of vinyl chlorides (eqs 5 and 6).10a,b

The stereospecific Pd/Cu-catalyzed cross-coupling reaction10,11 of terminal alkynes with (E)- or (Z)-1,2-dichloroethylene is a chemoselective and efficient route to (E) or (Z) conjugated chloroenynes or enediynes (eq 7).10b

Applications to the synthesis of esperamycins and related substances12 have been described (eq 8).12a

(Z)-Chloroenynes are converted into 1,3-diynes under mild conditions by treatment with Tetra-n-butylammonium Fluoride (eq 9).13

Selective reduction of enediynes, dienynes, and trienynes, prepared from 1,2-dichloroethylenes, allows for the stereocontrolled synthesis of conjugated trienes14 (eq 10)10b and tetraenes (eq 11)15 having a defined geometry.

Related Reagents.

1-Chloro-2-iodoethylene.


1. Köbrich, G. AG(E) 1965, 4, 49.
2. Köbrich, G. AG 1967, 79, 15.
3. Köbrich, G.; Flory, K. TL 1964, 1137 (CA 1964, 61, 3129f). Köbrich, G.; Flory, K. CB 1966, 99, 1773 (CA 1966, 65, 7203d).
4. Yamada, K.; Miyaura, N.; Itoh, M.; Suzuki, A. TL 1975, 1961.
5. (a) Loutfy, R. O.; de Mayo, P. CJC 1972, 50, 3465. (b) Tobe, Y.; Kakiuchi, K.; Kobiro, K.; Odaira, Y. S 1993, 460.
6. Truce, W. E.; Boudakian, M. M.; Heine, R. F.; McManimie, R. J. JACS 1956, 78, 2743.
7. Yamaji, M.; Fujiwara, Y.; Imanaka, T.; Teranishi, S. BCJ 1970, 43, 2659.
8. Aguiar, A. M.; Daigle, D. JACS 1964, 86, 2299.
9. (a) Corriu, R. J. P.; Masse, J. P. CC 1972, 144. (b) Tamao, K.; Sumitani, K.; Kumada, M. BCJ 1976, 49, 1958. (c) Okamoto, S.; Tani, K.; Sato, F.; Sharpless, K. B.; Zargarian, D. TL 1993, 34, 2509.
10. (a) Ratovelomanana, V.; Linstrumelle, G. TL, 1981, 22, 315. (b) Ratovelomanana, V.; Linstrumelle, G. TL 1984, 25, 6001. (c) Vollhardt, K. P. C.; Winn, L. S. TL 1985, 26, 709. (d) Guillerm, D.; Linstrumelle, G. TL 1985, 26, 3811. (e) Huynh, C.; Linstrumelle, G. T 1988, 44, 6337. (f) Crévisy, C.; Beau, J.-M. TL 1991, 32, 3171.
11. Alami, M.; Linstrumelle, G. TL 1991, 32, 6109.
12. (a) Magnus, P.; Carter, P.; Elliott, J.; Lewis, R.; Harling, J.; Pitterna, T.; Bauta, W. E.; Fortt, S. JACS, 1992, 114, 2544. (b) Smith, A. L.; Hwang, C. K.; Pitsinos, E.; Scarlato, G. R.; Nicolaou, K. C. JACS, 1992, 114, 3134. (c) Skrydstrup, T.; Audrain, H.; Ulibarri, G.; Grierson, D. S. TL 1992, 33, 4563. (d) Nicolaou, K. C.; Smith, A. L. AC(R) 1992, 25, 497.
13. Kende, A. S.; Smith, C. A. JOC 1988, 53, 2655.
14. (a) Guillerm, D.; Linstrumelle, G. TL 1986, 27, 5857. (b) Ratovelomanana, V.; Linstrumelle, G. BSF(2) 1987, 174 (CA 1988, 108, 5773n). (c) Chemin, D.; Linstrumelle, G. T 1992, 48, 1943. (d) Chemin, D.; Alami, M.; Linstrumelle, G. TL 1992, 33, 2681.
15. Alami, M.; Crousse, B.; Linstrumelle, G.; Mambu, L.; Larchevêque, M. SL 1993, 217.

Gérard Linstrumelle & Mouâd Alami

Ecole Normale Supérieure, Paris, France



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