Synthesis of unsaturated nine-membered ring ethers (Δ3-oxonenes) containing a Z- or E-configurated double bond: Thermodynamic versus kinetic control in palladium-catalyzed allylic cyclizations

Angewandte Chemie - International Edition

Volumn 37, Issue 5, 1998, Pages 633-635

  Pohlmann, Jens ^b   Sabater, Christopher ^c   Hoffmann, H M R ^a  

^a LEIBNIZ UNIVERSITY HANNOVER   (Germany)

^b CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

^c Dragoco Gerberding and Co AG   (Germany)

Author keywords

Allyl complexes; Cyclizations; Medium sized rings; Palladium

Indexed keywords

EID: 0031949287     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19980316)37:5<633::AID-ANIE633>3.0.CO;2-8     Document Type: Article

References (25)

1. a) M. C. Elliot, Contemp. Org. Synth. 1997, 4, 238-259;
2. b) ibid. 1994, 1, 457-474;
3. c) C. J. Moody, M. J. Davies in Studies in Natural Product Chemistry, Vol. 10 (Ed.: Atta-ur-Rahman), Elsevier, Amsterdam, 1992, pp. 201-239;
4. d) medium-ring lactones: G. Rousseau, Tetrahedron 1995, 51, 2777-2849.
5. CAS-online search up until August 1997.
6. A. Brandes, U. Eggert, H. M. R. Hoffmann, Synlett 1994, 745-747.
7. No attempt was made to control the third stereocenter by using enantiopure 1-pentyn-3-ol in the first step, since the configuration of this chiral center is partially lost on cyclization (Scheme 4).
8. For accounts of the extensive primary literature and Pd-mediated allylic alkylations see: a) J. Tsuji, Palladium Reagents and Catalysts. Innovations in Organic Synthesis, Wiley, Chichester, 1997; b) B. M. Trost, D. L. Van Vranken, Chem. Rev. 1996, 96, 395-422; c) C. G. Frost, J. Howarth, J. M. J. Williams, Tetrahedron: Asymmetry 1992, 3, 1089-1122; d) S. A. Godleski in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon, Oxford, 1991, pp. 585-661; e) B. M. Trost, Angew. Chem. 1989, 101, 1199-1219; Angew. Chem. Int. Ed. Engl. 1989, 28, 1173-1192.
9. For accounts of the extensive primary literature and Pd-mediated allylic alkylations see: a) J. Tsuji, Palladium Reagents and Catalysts. Innovations in Organic Synthesis, Wiley, Chichester, 1997; b) B. M. Trost, D. L. Van Vranken, Chem. Rev. 1996, 96, 395-422; c) C. G. Frost, J. Howarth, J. M. J. Williams, Tetrahedron: Asymmetry 1992, 3, 1089-1122; d) S. A. Godleski in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon, Oxford, 1991, pp. 585-661; e) B. M. Trost, Angew. Chem. 1989, 101, 1199-1219; Angew. Chem. Int. Ed. Engl. 1989, 28, 1173-1192.
10. For accounts of the extensive primary literature and Pd-mediated allylic alkylations see: a) J. Tsuji, Palladium Reagents and Catalysts. Innovations in Organic Synthesis, Wiley, Chichester, 1997; b) B. M. Trost, D. L. Van Vranken, Chem. Rev. 1996, 96, 395-422; c) C. G. Frost, J. Howarth, J. M. J. Williams, Tetrahedron: Asymmetry 1992, 3, 1089-1122; d) S. A. Godleski in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon, Oxford, 1991, pp. 585-661; e) B. M. Trost, Angew. Chem. 1989, 101, 1199-1219; Angew. Chem. Int. Ed. Engl. 1989, 28, 1173-1192.
11. For accounts of the extensive primary literature and Pd-mediated allylic alkylations see: a) J. Tsuji, Palladium Reagents and Catalysts. Innovations in Organic Synthesis, Wiley, Chichester, 1997; b) B. M. Trost, D. L. Van Vranken, Chem. Rev. 1996, 96, 395-422; c) C. G. Frost, J. Howarth, J. M. J. Williams, Tetrahedron: Asymmetry 1992, 3, 1089-1122; d) S. A. Godleski in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon, Oxford, 1991, pp. 585-661; e) B. M. Trost, Angew. Chem. 1989, 101, 1199-1219; Angew. Chem. Int. Ed. Engl. 1989, 28, 1173-1192.
12. For accounts of the extensive primary literature and Pd-mediated allylic alkylations see: a) J. Tsuji, Palladium Reagents and Catalysts. Innovations in Organic Synthesis, Wiley, Chichester, 1997; b) B. M. Trost, D. L. Van Vranken, Chem. Rev. 1996, 96, 395-422; c) C. G. Frost, J. Howarth, J. M. J. Williams, Tetrahedron: Asymmetry 1992, 3, 1089-1122; d) S. A. Godleski in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon, Oxford, 1991, pp. 585-661; e) B. M. Trost, Angew. Chem. 1989, 101, 1199-1219; Angew. Chem. Int. Ed. Engl. 1989, 28, 1173-1192.
13. For accounts of the extensive primary literature and Pd-mediated allylic alkylations see: a) J. Tsuji, Palladium Reagents and Catalysts. Innovations in Organic Synthesis, Wiley, Chichester, 1997; b) B. M. Trost, D. L. Van Vranken, Chem. Rev. 1996, 96, 395-422; c) C. G. Frost, J. Howarth, J. M. J. Williams, Tetrahedron: Asymmetry 1992, 3, 1089-1122; d) S. A. Godleski in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon, Oxford, 1991, pp. 585-661; e) B. M. Trost, Angew. Chem. 1989, 101, 1199-1219; Angew. Chem. Int. Ed. Engl. 1989, 28, 1173-1192.
14. Other names: 2,3,4,5,6,9-hexahydrooxonine, 3,4-didehydrooxonane.
15. -1 lower in energy than trans-cyclononene: J. M. Goodman, personal communication.
16. -1 lower in energy than trans-cyclononene: J. M. Goodman, personal communication.
17. -1 lower in energy than trans-cyclononene: J. M. Goodman, personal communication.
18. 1 intermediates, prior to nucleophihc addition. This is not the case here, which shows contra Curtin-Hammett behavior. For recent references to pertinent literature see J. D. Oslob, B. Åkermark, P. Helquist, P.-O. Norrby, Organometallics 1997, 16, 3015-3021; reference [5].
19. H. M. R. Hoffmann, A. Brandes, Tetrahedron 1995, 51, 155-164; see also A. Brandes, H. M. R. Hoffmann, ibid. 1995, 51, 145-154.
20. H. M. R. Hoffmann, A. Brandes, Tetrahedron 1995, 51, 155-164; see also A. Brandes, H. M. R. Hoffmann, ibid. 1995, 51, 145-154.
21. 2]. Consequently, palladium-induced allylic ether cleavage is suppressed and there is less isomerization from E-to Z-configurated cyclic ether.
22. H. Muth, M. Sauerbier, Methoden Org. Chem. (Houben-Weyl), Vol. 4/ 1c, 1980, pp. 664-665.
23. S. Chandrasekhar, J. Yu, J. R. Falck, C. Mioskowski, Tetrahedron Lett. 1994, 35, 5441.
24. R. D. Little, S. O. Myong, Tetrahedron Lett. 1980, 21, 3339.
25. J. Pohlmann, Dissertation, Universität Hannover, 1997.