Microwave-accelerated competing domino processes: A tether-controlled dual pathway into high molecular complexity

Organic Letters

Volumn 10, Issue 11, 2008, Pages 2219-2222

  Elkhayat, Zobida ^a   Safir, Imad ^a   Castellote, Isabel ^a   Retailleau, Pascal ^a   Arseniyadis, Siméon ^a  

^a CNRS   (France)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; ETHER; FUSED HETEROCYCLIC RINGS; LEAD ACETATE; ORGANOMETALLIC COMPOUND; PROPYLENE;

ARTICLE; CHEMISTRY; MICROWAVE RADIATION; TIME;

ALKENES; BICYCLO COMPOUNDS, HETEROCYCLIC; ETHER, ETHYL; MICROWAVES; ORGANOMETALLIC COMPOUNDS; TIME FACTORS;

EID: 52649087871     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol800639b     Document Type: Article

References (21)

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2. (a) Tietze, L. F.; Beifuss, U. Angew. Chem., Int. Ed. 1993, 32, 131-163.
3. (b) Tietze, L. F. Chem. Rev. 1996, 96, 115-136.
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5. Articles dealing with specific aspects of organolead chemistry: (a) Criegee, R. In Oxidation In Organic Chemistry; Wiberg, K. B., Ed.; Academic Press; New York, 1965; Part A, p 277-366.
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9. Obtained in quantity in our previous work, 1a served as common intermediate for the synthesis of all but two (16a, 16b) domino precursors in this study.
10. For the original procedure (reduction of acrylonitriles) see: (a) Profitt, J. A.; Watt, D. S.; Corey, E. J. J. Org. Chem. 1975, 40, 127-128.
11. Adapted to a,β,-unsaturated esters by: (b) Hudlicky, T.; Sinai-Zingde, G.; Natchus, M. G Tetrahedron Lett. 1987, 28, 5287-5290.
12. (a) Corbu, A.; Gauron, G.; Castro, J. M.; Dakir, M.; Arseniyadis, S. Org. Lett. 2007, 9, 4745-4748.
13. (b) Adler, M. E.; Yumagulova, S. A.; Torosyan, S. A.; Miftakhov, M. S. Russ. J. Org. Chem. 1994, 30, 1006-1007.
14. (c) Hanselmann, R.; Benn, M. Synth. Commun. 1996, 26, 945-961.
15. The entropic requirement to form an eight-membered cyclic oxonium intermediate renders the ring-retained path unlikely (ca. millionfold drop in reactivity from 5 to 8-membered ring formation). For entropic and enthalpic factors during the formation of medium-sized rings, see: Illuminati, G.; Mandolini, L Acc. Chem. Res. 1981, 14, 95-101.
16. (a) Kappe, C. O.; Stadler, A. Microwaves in Organic and Medicinal Chemistry; Wiley-VCH: Weinheim, 2005.
17. (b) Kappe, C. O.; Dallinger, D. Drug Discovery 2006, 5, 51-63.
18. Stereoelectronic control: PM3 calculated dihedral angle of 178° for a nearly ideal orbital alignment.
19. Formation of the 6-membered oxonium ion is slower than that of the 5-membered one (ca. two powers of ten drop in reactivity per added methylene, see ref 7).
20. The entropic requirement to form a seven-membered cyclic oxonium intermediate renders the ring-retained (oxonium) path unlikely.
21. 3 displacement, which completely dominates the ring expansion path.