Strained rings to assess the 'endo Preference' of 2-alkyl branched 2- alkenylpotassium species

Tetrahedron Letters

Volumn 39, Issue 23, 1998, Pages 4031-4034

  Kotthaus, Martina ^a   Schlosser, Manfred ^a  

^a UNIVERSITY OF LAUSANNE   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

POTASSIUM DERIVATIVE; TETRAHYDROFURAN; TRIMETHYLSILYLMETHYLPOTASSIUM; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL STRUCTURE; ISOMERISM; STRUCTURE ANALYSIS; THERMODYNAMICS;

EID: 0032482525     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)00689-3     Document Type: Article

References (26)

1. 1. Schlosser, M.; Hartmann, J.; David, V.; Helv. Chim. Acta 1974, 57, 1567-1576; Schlosser, M.; in Organometallics in Synthesis : A Manual (ed. : Schlosser, M.), Wiley, Chichester, 1994, pp. 1-166, spec. 76-77.
2. 1. Schlosser, M.; Hartmann, J.; David, V.; Helv. Chim. Acta 1974, 57, 1567-1576; Schlosser, M.; in Organometallics in Synthesis : A Manual (ed. : Schlosser, M.), Wiley, Chichester, 1994, pp. 1-166, spec. 76-77.
3. 2. Allylic and benzylic organometallic intermediates generated by treatment with the superbasic mixture of butyllithium and potassium tert-butoxide are predominantly organopotassium species [Schlosser, M.; Hartmann, J.; Angew. Chem. 1973, 85, 544-545; Angew. Chem. Int. Ed. Engl. 1973, 12, 508-509].
4. 2. Allylic and benzylic organometallic intermediates generated by treatment with the superbasic mixture of butyllithium and potassium tert-butoxide are predominantly organopotassium species [Schlosser, M.; Hartmann, J.; Angew. Chem. 1973, 85, 544-545; Angew. Chem. Int. Ed. Engl. 1973, 12, 508-509].
5. 3. Schlosser, M.; Desponds, O.; Lehmann, R.; Moret, E.; Rauchschwalbe, G.; Tetrahedron 1993, 49, 10175 -10203.
6. 4. The metalation of caryophyllene with a stoichiometric amount of virtually solvent-free butyllithium in the presence of N,N,N′,N′-tetramethylethylene followed by quenching with heavy water has been reported to afford roughly 10% deuterated caryophyllene and 40% of deuterated isocaryophyllene, 50% of unconsumed starting material being recovered [Garner, C.M.; Thomas, A.A.; J. Org. Chem. 1995, 60, 7051-7054].
7. 5. Rauchschwalbe, G.; Schlosser, M.; Helv. Chim. Acta 1975, 55, 1094-1099.
8. 6. Hinkley, S.F.R.; Perry, N.B.; Weavers, R.T.; Phytochemistry 1994, 35, 1489-1494; Tetrahedron Lett. 1994, 35, 3775-3776; s.a. : Chhabra, B.R.; Hayano, K.; Ohtsuka, T.; Shirahama, H.; Matsumoto, T.; Chem. Lett. 1981, 1703-1706.
9. 6. Hinkley, S.F.R.; Perry, N.B.; Weavers, R.T.; Phytochemistry 1994, 35, 1489-1494; Tetrahedron Lett. 1994, 35, 3775-3776; s.a. : Chhabra, B.R.; Hayano, K.; Ohtsuka, T.; Shirahama, H.; Matsumoto, T.; Chem. Lett. 1981, 1703-1706.
10. 6. Hinkley, S.F.R.; Perry, N.B.; Weavers, R.T.; Phytochemistry 1994, 35, 1489-1494; Tetrahedron Lett. 1994, 35, 3775-3776; s.a. : Chhabra, B.R.; Hayano, K.; Ohtsuka, T.; Shirahama, H.; Matsumoto, T.; Chem. Lett. 1981, 1703-1706.
11. 7. Barrero, A.F.; Sánchez, J.F.; Oltra, J.E.; Altarejos, J.; Ferrol, N.; Barragán, A.; Phytochemistry 1991, 30, 1551-1554; Barrero, A.F.; Molina, J.; Oltra, J.E.; Altarejos, J.; Barragán, A.; Lara, A.; Segura, M.; Tetrahedron 1995, 51, 3813-3822; s.a. : Barrero, A.F.; Sánchez, J.F.; Ferrol, N.; San Feliciano, A.; Tetrahedron Lett. 1989, 30, 247-250.
12. 7. Barrero, A.F.; Sánchez, J.F.; Oltra, J.E.; Altarejos, J.; Ferrol, N.; Barragán, A.; Phytochemistry 1991, 30, 1551-1554; Barrero, A.F.; Molina, J.; Oltra, J.E.; Altarejos, J.; Barragán, A.; Lara, A.; Segura, M.; Tetrahedron 1995, 51, 3813-3822; s.a. : Barrero, A.F.; Sánchez, J.F.; Ferrol, N.; San Feliciano, A.; Tetrahedron Lett. 1989, 30, 247-250.
13. 7. Barrero, A.F.; Sánchez, J.F.; Oltra, J.E.; Altarejos, J.; Ferrol, N.; Barragán, A.; Phytochemistry 1991, 30, 1551-1554; Barrero, A.F.; Molina, J.; Oltra, J.E.; Altarejos, J.; Barragán, A.; Lara, A.; Segura, M.; Tetrahedron 1995, 51, 3813-3822; s.a. : Barrero, A.F.; Sánchez, J.F.; Ferrol, N.; San Feliciano, A.; Tetrahedron Lett. 1989, 30, 247-250.
14. [7] : δ 5.53 (1 H, t, J 7.8), 4.84 (1 H, d, J 1.8), 4.75 (1 H, m), 4.03 (2 H, s), 2.51 (1 H, q, J 9.1), 2.2 (6 H, m), 1.82 (1 H, ddd, J 11.4, 9.1, 3.9), 1.73 (1 H, dd, J 10.8, 8.7), 1.5 (4 H, m), 1.00 (3 H, s), 0.96 (3 H, s).
15. 5, 400 MHz) of E-2 : δ 5.40 (0.75 × 1 H, dd, J 10.2, 5.2), 5.26 (0.25 × 1 H, d, J 11.0), 5.08 (1 H, d, J 0.8), 4.95 (0.25 × 1 H, s), 4.92 (0.75 × 1 H, s), 2.2 (7 H, m), 1.78 (3 H, symm. m), 1.67 (0.25 × 3 H, s), 1.64 (0.75 × 3 H, s), 1.5 (2 H, m), 1.09 (0.75 × 3 H, s), 1.07 (0.25 × 3 H, s), 1.03 (3 H, s).
16. 10. Conditions : 30 m capillary, silicon rubber DB-1701, 80 °C [10 min, then 10 °C increase/min] → 200 °C [10 min]; 2 m packed glass column, 8% Carbowax 20M, 80 °C [10 min, then 10 °C increase/min] → 180 °C [10 min]; internal standard : undecane.
17. 11. Hartmann, J., Schlosser, M.; Synthesis 1975, 328-329; Helv. Chim. Acta 1976, 59, 453-466.
18. 11. Hartmann, J., Schlosser, M.; Synthesis 1975, 328-329; Helv. Chim. Acta 1976, 59, 453-466.
19. 12. Stähle, M.; Schlosser, M.; J. Organomet. Chem. 1981, 220, 277-283.
20. 13. Dauben, W.G.; Pitzer, K.S.; in Steric Effects in Organic Chemistry (ed. : Newman, M.S.), Wiley, New York, 1956, p. 58; Eliel, E.L.; Stereochemistry of Carbon Compounds, McGraw Hill, New York 1962, p. 339.
21. 13. Dauben, W.G.; Pitzer, K.S.; in Steric Effects in Organic Chemistry (ed. : Newman, M.S.), Wiley, New York, 1956, p. 58; Eliel, E.L.; Stereochemistry of Carbon Compounds, McGraw Hill, New York 1962, p. 339.
22. 14. Hübner, M.; Rissom, B.; Fitjer, L.; Helv. Chim. Acta 1997, 80, 1972-1982; and personal communication (of 6 Nov. 1997) to the senior author.
23. 15. Ref. 7c and personal communication (of 17 Nov. 1997) to the senior author.
24. 16. Peyerimhoff, S.D.; Buenker, R.J.; J. Chem. Phys. 1969, 51, 2528-2537; Schleyer P.V.R., J. Am. Chem. Soc. 1985, 107, 4793-4794; Boche, G.; Fraenkel, G.; Cabral, J.; Harms, K.; van Eikema Hommes, N.J.R.; Lohrenz, J.; Marsch, M.; Schleyer, P.V.R.; J. Am. Chem. Soc. 1992, 114, 1562-1565.
25. 16. Peyerimhoff, S.D.; Buenker, R.J.; J. Chem. Phys. 1969, 51, 2528-2537; Schleyer P.V.R., J. Am. Chem. Soc. 1985, 107, 4793-4794; Boche, G.; Fraenkel, G.; Cabral, J.; Harms, K.; van Eikema Hommes, N.J.R.; Lohrenz, J.; Marsch, M.; Schleyer, P.V.R.; J. Am. Chem. Soc. 1992, 114, 1562-1565.
26. 16. Peyerimhoff, S.D.; Buenker, R.J.; J. Chem. Phys. 1969, 51, 2528-2537; Schleyer P.V.R., J. Am. Chem. Soc. 1985, 107, 4793-4794; Boche, G.; Fraenkel, G.; Cabral, J.; Harms, K.; van Eikema Hommes, N.J.R.; Lohrenz, J.; Marsch, M.; Schleyer, P.V.R.; J. Am. Chem. Soc. 1992, 114, 1562-1565.