Iodine-Zinc Exchange Reactions Mediated by i-Pr2Zn. A New Preparation of Secondary Zinc Reagents

Synlett

Volumn 1997, Issue 3, 1997, Pages 327-328

  Micouin, Laurent ^a   Knochel, Paul ^a  

^a PHILIPPS UNIVERSITY MARBURG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0002249396     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1997-760     Document Type: Article

References (26)

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2. (b) Gilman, H.; Langham, W.; Jacoby, A. L. J. Am. Chem. Soc. 1939, 61, 106.
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7. (d) Villieras, J. Organomet. Chem. Rev. A. 1971, 7, 71.
8. (a) Rozema, M. J.; AchyuthaRao, S.; Knochel, P. J. Org. Chem. 1992, 57, 1956.
9. (b) Rozema, M. J.; Eisenberg, C.; Lütjens, H.; Belyk, K.; Knochel, P. Tetrahedron Lett. 1993, 34, 3115.
10. (c) Knochel, P. Synlett, 1995, 393.
11. (a) Brieden, W.; Ostwald, R.; Knochel, P. Angew. Chem. Int. Ed. Engl. 1993, 105, 629.
12. (b) Lütjens, H.; Knochel, P. Tetrahedron: Asymmetry 1994, 5, 1161.
13. (c) Eisenberg, C.; Knochel, P. J. Org. Chem. 1994, 59, 3769.
14. (d) Vettel, S.; Knochel, P. Tetrahedron Lett. 1994, 35, 5849.
15. (e) Knochel, P.; Vettel, S.; Eisenberg, C. Appl. Organomet. Chem. 1995, 9, 175.
16. 2 followed by distillation under argon atmosphere (bp 55°C , 100 mbar).
17. Knochel, P.; Yeh, M. C. P.; Berk, S. C.; Talbert, J. J. Org. Chem. 1988, 53, 2390.
18. Villieras, J.; Rambaud, M. Synthesis 1982, 924.
19. Yeh, M. C. P.; Knochel, P. Tetrahedron Lett. 1989, 30, 4799.
20. Micouin, L.; Oestreich, M.; Knochel, P. Angew. Chem. 1997, 109, in press.
21. Oshikawa, T.; Yamashita, M. Bull Chem. Soc. Jpn. 1984, 57, 2675.
22. No general preparation of secondary diorganozincs has been reported. For some examples see: (a) Nützet, K. in Methoden der Organischen Chemie, Vol. 13/2a, p. 592, Thieme, Stuttgart 1973. (b) Langer, F.; Schwink, L;. Devasagayaraj, A.; Chavant, P.-Y.; Knochel, P.; J. Org. Chem. 1996, 61, 8229. However, secondary alkyl/inc halides are available: (c) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117. (d) Hanson, M. V.; Rieke, R. D. J. Am. Chem. Soc. 1995, 117, 10775.
23. No general preparation of secondary diorganozincs has been reported. For some examples see: (a) Nützet, K. in Methoden der Organischen Chemie, Vol. 13/2a, p. 592, Thieme, Stuttgart 1973. (b) Langer, F.; Schwink, L;. Devasagayaraj, A.; Chavant, P.-Y.; Knochel, P.; J. Org. Chem. 1996, 61, 8229. However, secondary alkyl/inc halides are available: (c) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117. (d) Hanson, M. V.; Rieke, R. D. J. Am. Chem. Soc. 1995, 117, 10775.
24. No general preparation of secondary diorganozincs has been reported. For some examples see: (a) Nützet, K. in Methoden der Organischen Chemie, Vol. 13/2a, p. 592, Thieme, Stuttgart 1973. (b) Langer, F.; Schwink, L;. Devasagayaraj, A.; Chavant, P.-Y.; Knochel, P.; J. Org. Chem. 1996, 61, 8229. However, secondary alkyl/inc halides are available: (c) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117. (d) Hanson, M. V.; Rieke, R. D. J. Am. Chem. Soc. 1995, 117, 10775.
25. No general preparation of secondary diorganozincs has been reported. For some examples see: (a) Nützet, K. in Methoden der Organischen Chemie, Vol. 13/2a, p. 592, Thieme, Stuttgart 1973. (b) Langer, F.; Schwink, L;. Devasagayaraj, A.; Chavant, P.-Y.; Knochel, P.; J. Org. Chem. 1996, 61, 8229. However, secondary alkyl/inc halides are available: (c) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117. (d) Hanson, M. V.; Rieke, R. D. J. Am. Chem. Soc. 1995, 117, 10775.
26. iC (0.1 mmHg), dissolved in THF (20 mL) and added to the previously prepared solution of the zinc reagent. 2-Bromo-1-phenylacetylene (3.6 g, 20 mmol) was added at -78°C. The reaction mixture was slowly allowed to warm to rt and was worked up as usual affording a crude oil which was purified by flash chromatography (hexanes) providing the product 4b (1.0 g, 5.4 mmol, 62% yield). b) Preparation of ethyl 2-(methylcydohexyl)acrylate (4a). (Method B; entry 1 of Table 1). A solution of isopropylmagnesium bromide (48 mL, 29.0 mmol, 0.6 M in ether, 3 equiv) was added to zinc bromide (3.56 g. 14.5 mmol) under argon atmosphere. The reaction mixture was stirred for 0.5 h at rt leading to a clear solution. Cyclohexyl iodide (2.0 g, 9.6 mmol) was added. The reaction mixture was stirred for 1 h at rt and a THF solution of CuCN · 2LiCl (20 mmol, prepared as described above) was added at -78°C followed by the addition of ethyl (α-bromomethyl)acrylate (5.80 g, 30 mmol). The reaction mixture was warmed up to 0°C and was worked up as usual affording after flash chromatography (ether / hexanes) the product 4a (1.20 g, 6.10 mmol. 64% yield).