[40207-59-8]  · C4H7LiO  · 1-Ethoxyvinyllithium  · (MW 78.04)

(reacts with aldehydes and ketones to form allylic alcohols;1,2 adds to the carbon-nitrogen double bond of isoquinolinium salts;3 reacts with chlorosilanes;4 can add to conjugated sulfones5)

Physical Data: 13C NMR solution studies in THF have been reported.6

Solubility: sol THF.

Form Supplied in: prepared in situ and used directly.

Preparative Methods: prepared in situ under nitrogen by the reaction of Ethyl Vinyl Ether in anhydrous THF with t-Butyllithium.

Handling, Storage, and Precautions: must be prepared and transferred under inert gas (Ar or N2) to exclude oxygen and moisture.

Additions to Aldehydes and Ketones.

1-Ethoxyvinyllithium adds to benzaldehyde to yield an allylic alcohol (eq 1) which, upon acid hydrolysis, forms the a-hydroxy methyl ketone.2 Reaction also occurs with ketones (eq 2).7

g-Ethoxy dienones have been synthesized in good yields via the intermediate produced by the reaction of 1-ethoxyvinyllithium with 3-ethoxy-2-cyclohexenones.8

Addition of the reagent to a 2-dialkylaminocyclohexanone has been reported (eq 3).9

The reagent adds to conjugated enones at the carbonyl group (eq 4).10-12

Addition of the reagent to an aldehyde in the total synthesis of nikkomycin B produced the vinyl ether, which was not isolated.13 The reagent can also be used to prepare the corresponding cuprate, which adds 1,4 to enones.14

Addition to Carbon-Nitrogen Double Bonds.

The reagent adds cleanly to isoquinolinium salts (eq 5) to yield, after acid hydrolysis, the methyl ketone.3

Reaction with Chlorosilanes.

Chlorosilanes react with 1-ethoxyvinyllithium4,15 to yield, after acid hydrolysis, acylsilanes with overall yields of 19-31% (eq 6).4

Addition to Conjugated Sulfones.

The reagent adds to conjugated sulfones at the b-carbon in good yields (eq 7).5

Related Reagents.

5-Lithio-2,3-dihydrofuran; 6-Lithio-2,3-dihydro-4H-pyran; 1-Methoxyvinyllithium.

1. (a) Lever, O. W., Jr. T 1976, 32, 1943. (b) Gschwend, H. W.; Rodriquez, H. R. OR 1979, 26, 1.
2. Schöllkopf, U.; Hänssle, P. LA 1972, 763, 208.
3. Tietze, L. F.; Brill, G. LA 1987, 311.
4. Bienz, S.; Chapeaurouge, A. HCA 1991, 74, 1477.
5. Isobe, M.; Funabashi, Y.; Ichikawa, Y., Mio, S.; Goto, T. TL 1984, 25, 2021.
6. Oakes, F. T.; Sebastian, J. F. JOC 1980, 45, 4959.
7. Modi, S. P.; Michael, M. A.; Archer, S.; Carey, J. J. T 1991, 47, 6539.
8. Kraus, G. A.; Krolski, M. E. SC 1982, 12, 521.
9. Jacobsen, E. J.; Levin, J.; Overman, L. E. JACS 1988, 110, 4329.
10. Kanda, Y.; Saito, H.; Fukuyama, T. TL 1992, 33, 5701.
11. Braish, T. F.; Saddler, J. C.; Fuchs, P. L. JOC 1988, 53, 3647.
12. Kallmerten, J.; Plata, D. J. H 1987, 25, 145.
13. Barrett, A. G. M.; Lebold, S. A. JOC 1990, 55, 5818.
14. Boeckman, R. K., Jr.; Bruza, K. J. JOC 1979, 44, 4781.
15. Cunico, R. F.; Kuan, C.-P. JOC 1985, 50, 5410.

John F. Sebastian

Miami University, Oxford, OH, USA

Copyright 1995-2000 by John Wiley & Sons, Ltd. All rights reserved.