1-Propenyllithium1

(E)

[6386-72-7]  · C3H5Li  · 1-Propenyllithium  · (MW 48.02) (Z)

[6524-17-0]

(precursor of propenyl metals2)

Physical Data: 1H and 13C NMR spectra have been reported.2g

Preparative Methods: prepared by reaction of 1-chloro- or 1-bromopropene with Lithium powder (containing 2% of sodium in the case of the chloride) in diethyl ether (eqs 1 and 2).4 This reaction occurs with a slight loss of stereochemistry.4d The reagent can also be prepared by metal-halogen exchange reaction between 1-bromopropene and t-Butyllithium (eq 3),5 and by transmetalation of tin derivatives by an organolithium compound (eq 4).2g,6 In the two latter cases, the reactions are stereospecific.

Handling, Storage, and Precautions: the solution of propenyllithium in diethyl ether must be handled with care since it is flammable and may ignite on contact with moisture and air. It should be stored and handled in an inert atmosphere (argon) and measured or transferred by means of a hypodermic syringe or cannula. The solution may deteriorate with time and the concentration of the reagent should be titrated before use.3

General Discussion.

Both (Z)- and (E)-1-propenyllithium reagents react with various electrophiles2g,4-6 with retention of configuration (eqs 5 and 6).7,8

When treated with 2-halogenoalkyl boronates in diethyl ether, (Z)- or (E)-1-propenyllithium leads to allyl boronates (eqs 7 and 8).9

The reaction of (Z)- or (E)-1-propenyllithium with Copper(I) Iodide or silver iodide leads to the corresponding organometallic compound which undergoes thermal decomposition to give 2,4-hexadiene with retention of configuration at the double bonds (eq 9).4d,f

Pure (Z)- and (E)-1-propenylcuprates, prepared according to standard cuprate procedures,2 undergo conjugate addition to a,b-unsaturated carbonyl compounds10 (eqs 10 and 11)10a and react readily with alkyl halides (eq 12)11 and epoxides (eq 13).12

When treated with allylic chlorides (e.g. (E)-1-chloro-2-octene), they lead to skipped dienes without isomerization or rearrangement (eq 14).13

Addition of (E)-1-propenylcuprate to a-hydroxy aldehydes in the presence of Magnesium Bromide etherate proceeds stereoselectively to give allylic alcohols (eq 15).14

The transmetalation of 1-propenyllithium with tributyltin bromide allows the preparation of 1-propenyltributyltin with retention of configuration (eq 16).15

In the presence of lithiated (+)-N-methylephedrine or (+)-2-(dimethylamino)-1,2-diphenylethanol, (Z)-1-propenylzinc bromide (prepared by transmetalation of (Z)-1-propenyllithium) adds enantioselectively to a variety of aldehydes (eq 17).16

Related Reagents.

(E)- and (Z)-alkenyllithium derivatives, prepared in the same way as (E)- and (Z)-propenyllithium reagents, are useful precursors of alkenyl organometallic compounds, particularly alkenyl cuprates.

Alkenylmanganese compounds, obtained by transmetalation of organolithium derivatives with manganese halides, are chemoselective reagents and react with acid chlorides to give a,b-unsaturated ketones (eq 18).17 Under copper catalysis, they add to a,b-unsaturated ketones in 1,4-fashion (eq 19).18

Alkenyllithium reagents bearing an alcohol function in the allylic position6a are useful intermediates in synthesis2f (eq 20).19 The corresponding cuprates react regioselectively with epoxides (eq 21).20

(E)-3-Hydroxy-1-octenyllithium is a key intermediate in prostaglandin synthesis.21 Several convenient approaches to prostaglandins commence with a preformed cyclopentane nucleus bearing suitable functionality for elaboration of at least one of the side chains. The second chain may be attached by a variety of methods. However, by far the most successful approach involves the conjugate addition of a vinyl copper to a cyclopentenone precursor (eq 22).22

Related Reagents.

Isopropenyllithium; Vinyllithium.


1. (a) Stowell, J. C. Carbanions in Organic Synthesis; Wiley: New York, 1979. (b) Negishi, E. I. Organometallics in Organic Synthesis; Wiley: New York, 1980.
2. (a) Posner, G. H. OR 1972, 19, 1. (b) Posner, G. H. OR 1975, 22, 253. (c) Normant, J. F. S 1972, 63. (d) Lipshutz, B. H. S 1987, 325. (e) Lipshutz, B. H. COS 1991, 1, 107. (f) Lipshutz, B. H.; Sengupta, S. OR 1992, 41, 135. (g) Seyferth, D.; Vaughan, L. G. JACS 1964, 86, 883. (h) van Dongen, J. P. C. M.; van Dijkman, H. W. D.; de Bie, M. J. A. RTC 1974, 93, 29.
3. Watson, S. C.; Eastham, J. F. JOM 1967, 9, 165.
4. (a) Braude, E. A.; Coles, J. A. JCS 1951, 2078. (b) Nesmeyanov, A. N.; Borisov, A. E. T 1957, 1, 158. (c) Curtin, D. Y.; Crump, J. W. JACS 1958, 80, 1922. (d) Whitesides, G. M.; Casey, C. P.; Krieger, J. K. JACS 1971, 93, 1379. (e) Linstrumelle, G. TL 1974, 3809. (f) Whitesides, G. M.; SanFilippo, J., Jr.; Casey, C. P.; Panek, E. J. JACS 1967, 89, 5302.
5. Neumann, H.; Seebach, D. TL 1976, 4839.
6. (a) Corey, E. J.; Wollenberg, R. H. JOC 1975, 40, 2265. (b) Piers, E.; Karunaratne, V. JOC 1983, 48, 1774.
7. Millon, J.; Lorne, R.; Linstrumelle, G. S 1975, 434.
8. Auvray, P.; Knochel, P.; Normant, J. F. T 1988, 44, 4509.
9. Roush, W. R.; Adam, M. A.; Walts, A. E.; Harris, D. J. JACS 1986, 108, 3422.
10. (a) Näf, F.; Degen, P. HCA 1971, 54, 1939. (b) Casey, C. P.; Boggs, R. A. TL 1971, 2455. (c) Smith, A. B., III; Huryn, D. M. JOC 1985, 50, 1342. (d) Oppolzer, W.; Mills, R. J.; Pachinger, W.; Stevenson, T. HCA 1986, 69, 1542.
11. Linstrumelle, G.; Krieger, J. K.; Whitesides, G. M. OS 1976, 55, 103.
12. Lipshutz, B. H.; Barton, J. C. JOC 1988, 53, 4495.
13. van Mourik, G. L.; Pabon, H. J. J. TL 1978, 2705.
14. (a) Gould, T. J.; Balestra, M.; Wittman, M. D.; Gary, J. A.; Rossano, L. T.; Kallmerten, J. JOC 1987, 52, 3889. (b) Kozikowski, A. P.; Lee, J. JOC 1990, 55, 863.
15. Seyferth, D.; Vaughan, L. G. JOM 1963, 1, 138.
16. Oppolzer, W.; Radinov, R. N. TL 1991, 32, 5777.
17. Cahiez, G.; Chavant, P. Y.; Metais, E. TL 1992, 33, 5245.
18. Cahiez, G.; Alami, M. TL 1989, 30, 3541.
19. Posner, G. H.; Kogan, T. P.; Haines, S. R.; Frye, L. L. TL 1984, 25, 2627.
20. Ohfune, Y.; Kurokawa, N. TL 1984, 25, 1587.
21. (a) Bindra, J. S. In The Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1981; Vol. 4, p 353. (b) Noyori, R.; Suzuki, M. AG 1984, 23, 847.
22. Johnson, C. R.; Penning, T. D. JACS 1988, 110, 4726.

Gérard Linstrumelle & Mouâd Alami

Ecole Normale Supérieure, Paris, France



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