Palladium-catalyzed [3 + 2] intramolecular cycloaddition of alk-5-enylidenecyclopropanes

Journal of the American Chemical Society

Volumn 128, Issue 2, 2006, Pages 384-385

  Gulías, Moisés ^a   García, Rebeca ^a   Delgado, Alejandro ^a   Castedo, Luis ^a   Mascareñas, José L ^a  

^a UNIVERSITY OF SANTIAGO DE COMPOSTELA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPROPANE DERIVATIVE; PALLADIUM;

ANNULATION REACTION; ARTICLE; CATALYSIS; CYCLOADDITION; MOLECULAR INTERACTION; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOCHEMISTRY; STEREOISOMERISM; STRUCTURE ANALYSIS;

EID: 31544445030     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja054487t     Document Type: Article

References (21)

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2. (b) Yamago, S.; Nakamura, E. Org. React. 2002, 61, 1-217.
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4. (d) Nakamura, E.; Yamamoto, Y. Adv. Svnth. Catal. 2002, 344, 111-129.
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6. Delgado, A.; Rodríguez, J. R.; Castedo, L.; Mascareñas, J. L. J. Am. Chem. Soc. 2003, 125, 9282-9283.
7. (a) Yamago, S.; Nakamura, E. J. Chem. Soc., Chem. Commun. 1988, 1112-1113.
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10. (b) Corlay, H.; Motherwell, W. B.; Pennel, A. M. K.; Shipman, M.; Slawin, A. M. Z.; Williams, D. J. Tetrahedron 1996, 52, 4883-4902.
11. (c) Lautens, M.; Ren, Y. J. Am. Chem. Soc. 1996, 118, 10668-10669.
12. (a) Stolle, A.; Ollivier, J.; Piras, P. P.; Salaün, J.; de Meijere, A. J. Am. Chem. Soc. 1992, 114, 4051-4067.
13. (b) Delogu, G.; Salaün, J.; de Candia, C.; Fabri, D.; Piras, P. P.; Ollivier, J. Synthesis 2002, 2271-2279 and references therein.
14. The synthesis of substrates 1, described in the Supporting Information, was accomplished by Pd-catalyzed alkylation of allylcyclopropyltosylate with the sodium salt of diethyl malonate, followed by alkylation with appropriate allylic bromides.
15. (a) Trost, B. M.; Chan, D. M. T. J. Am. Chem. Soc. 1982, 104, 3733-3734.
16. (b) Trost, B. M.; Greese, T. A.; Chan, D. M. T. J. Am. Chem. Soc. 1991, 113, 7350-7362.
17. (a) Trost, B. M. Angew. Chem., Int. Ed. Engl. 1986, 25, 1-20.
18. (b) For a discussion of the mechanism of these cycloadditions, see: Singleton, D. A.; Schulmeier, B. E. J. Am. Chem. Soc. 1999, 121, 9313-9317.
19. Partial loss of stereospecificity has previously been observed in cycloadditions between activated cis-alkenes and Pd-TMM species generated from bifunctional reagents: Trost, B. M.; Chan, D. M. T. J. Am. Chem. Soc. 1983, 105, 2315-2325. See also ref 4b.
20. The lack of reactivity seems to be associated with the substrate structure rather than to the presence of a CN group because the cycloaddition of Ia is inhibited by the presence of 1 equiv of 1c but not by the addition of excess of valeronitrile.
21. The calculations were carried out with the Gaussian 98 set of programs using the B3LYP hybrid functional to perform vibrational analysis, characterize stationary points, and determine zero-point energies (ZPE). Whereas the transition state corresponding to the carbometalation step in path 1 for model system 12 is 28.7 kcal/mol above palladacyclobutane A, TS2 for the E-alkene is only 16.4 kcal/mol higher in energy than A. On the other hand, the activation energy required to convert A (with a Z-alkene geometry) into D through TS3 is 14.5 kcal/mol. Further computational details are described in the Supporting Information, and full details will be reported in due course.