Olefinic stereoselection in the [2,3]-Wittig rearrangement of α,β- disubstituted allylic ethers forming trisubstituted olefins

Tetrahedron Letters

Volumn 40, Issue 34, 1999, Pages 6257-6260

  Tomooka, Katsuhiko ^a   Igarashi, Tatsuya ^a   Kishi, Naoyuki ^a   Nakai, Takeshi ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

2,3 Wittig rearrangement; Olefinic stereoselection; Z trisubstituted olefins

Indexed keywords

ALKENE DERIVATIVE; ALLYL COMPOUND; ETHER DERIVATIVE; SILANE DERIVATIVE;

ARTICLE; CHEMICAL MODIFICATION; CHEMICAL STRUCTURE; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0033588315     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01195-8     Document Type: Article

References (17)

1. Reviews: Nakai, T.; Mikami, K. Chem. Rev. 1986, 86, 885-902. Nakai, T.; Mikami, K. Org. React. 1994, 46, 105-209. Marshall, J. A. In Comprehensive Organic Synthesis; Trost, B. M.; Fleming, I, Eds.; Pergamon: New York, 1991; Vol. 3, pp. 975-1014.
2. Reviews: Nakai, T.; Mikami, K. Chem. Rev. 1986, 86, 885-902. Nakai, T.; Mikami, K. Org. React. 1994, 46, 105-209. Marshall, J. A. In Comprehensive Organic Synthesis; Trost, B. M.; Fleming, I, Eds.; Pergamon: New York, 1991; Vol. 3, pp. 975-1014.
3. Reviews: Nakai, T.; Mikami, K. Chem. Rev. 1986, 86, 885-902. Nakai, T.; Mikami, K. Org. React. 1994, 46, 105-209. Marshall, J. A. In Comprehensive Organic Synthesis; Trost, B. M.; Fleming, I, Eds.; Pergamon: New York, 1991; Vol. 3, pp. 975-1014.
4. Still, W. C; Mitra, A. J. Am. Chem. Soc. 1978, 100, 1927-1928. For the reductive lithiation variant: Kruse, B.; Brückner, R. Chem. Ber. 1989, 122, 2023-2025.
5. Still, W. C; Mitra, A. J. Am. Chem. Soc. 1978, 100, 1927-1928. For the reductive lithiation variant: Kruse, B.; Brückner, R. Chem. Ber. 1989, 122, 2023-2025.
6. Kaye, A. D.; Pattenden, G.; Roberts, S. M. Tetrahedron Lett. 1986, 27, 2033-2036.
7. 3 are trans) for the sake of consistency. Thus, note that 'E' corresponds to Z (by the usual convention).
8. Mikami, K.; Kishi, N.; Nakai, T. Chem. Lett. 1982, 1643-1646.
9. For other Z-selective variants with different G groups, consult Ref. 1.
10. (a) Tomooka, K.; Igarashi, T.; Watanabe, M.; Nakai, T. Tetrahedron Lett. 1992, 33, 5795-5798.
11. (b) Tomooka, K.; Igarashi, T.; Nakai, T. Tetrahedron 1994, 50, 5927-5932.
12. 3) for 1-H, 3.69 (dd, J=5.8, 7.4 Hz) for 1a and 3.47 (dd, J=6.4,7.4 Hz) for 1b.
13. 1H NMR, δ 0.88 (t, J=7.2 Hz, 3H), 0.98 (t, 7.4 Hz, 3H), 1.10-1.42 (m, 8H), 1.59 (br. s, 1H), 1.68 (s, 3H), 2.04 (ddd, J=4.4, 8.5, 10.5 Hz, 1H), 3.34-3.42 (m, 1H), 4.81-4.84 (m, 1H), 4.95-4.98 (m, 1H).
14. Note that the [2,3]-Wittig rearrangement is well-established to proceed with complete inversion of configuration at the Li-bearing terminus (Ref. 7a).
15. (a) Chan, T. H.; Mychajlowskij, W.; Amouroux, R. Tetrahedron Lett. 1977, 1605-1608.
16. 1H NMR spectra of product 5, the olefinic proton of the 'Z'-isomer appears at a higher field than that of the 'E'-isomer; e.g., 5a (entry 1), δ 6.09 (q) vs. 6.17 (q); 5d (entry 5), δ 6.09 (q) vs. 6.20 (q); 5e (entry 6), δ 6.07 (q) vs. 6.29 (q); 5f (entry 7), δ 6.34 (q) vs. 6.69 (q); 5g (entry 8), δ 5.96 (t) vs. 6.12 (t); 5h (entry 9), δ 5.72 (d); 5i (entry 10), δ 6.01 (q).
17. Mikami, K.; Azuma, K.; Nakai, T. Tetrahedron 1984, 40, 2303-2308.