[Ind2TiMe2]: A catalyst for the hydroaminomethylation of alkenes and styrenes

Angewandte Chemie - International Edition

Volumn 49, Issue 14, 2010, Pages 2626-2629

  Kubiak, Raphael ^a   Prochnow, Insa ^a   Doye, Sven ^a  

^a UNIVERSITY OF OLDENBURG   (Germany)

Author keywords

Alkenes; Amines; C H activation; Homogeneous catalysis; Titanium

Indexed keywords

C-H ACTIVATION; CH-BOND ACTIVATION; CHEMICAL EQUATIONS; HOMOGENEOUS CATALYSIS; HYDROAMINOMETHYLATION; INDENYL;

ACTIVATION ANALYSIS; AMINES; CATALYSIS; CATALYSTS; CHEMICAL BONDS; REACTION KINETICS; STYRENE; TITANIUM;

OLEFINS;

ALKENE; AMINE; STYRENE DERIVATIVE; TITANIUM;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY;

ALKENES; AMINES; CATALYSIS; MOLECULAR STRUCTURE; STYRENES; TITANIUM;

EID: 77950204427     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.200906557     Document Type: Article

References (18)

1. For a recent review on hydroamination of alkenes and alkynes, see: T. E. Müller, K. C. Hultzsch, M. Yus. F. Foubelo. M. Tada, Chem. Rev. 2008, 108, 3795-3892.
2. Review: P. W. Roesky, Angew. Chem. 2009, 121, 4988-4991;
3. Angew. Chem. Int. Ed. 2009, 48, 4892-4894.
4. a) M. G. Clerici, F. Maspero, Synthesis 1980, 305-306;
5. b) W. A. Nugent, D. W. Ovenall, S. J. Holmes, Organometallics 1983, 2, 161-162.
6. a) S. B. Herzon. J. F. Hartwig, J. Am. Chem. Soc. 2007, 129, 6690-6691;
7. b) S. B. Herzon, J. F. Hartwig, J. Am. Chem. Soc. 2008, 130, 14940-14941.
8. P. Eisenberger, R. O. Ayinla, J. M. P. Lauzon, L. L. Schafer, Angew. Chem. 2009, 121, 8511-8515:
9. Angew. Chem. Int. Ed. 2009, 48, 8361-8365.
10. a) R. Kubiak, I. Prochnow, S. Doye, Angew. Chem 2009, 121, 1173-1176;
11. Angew. Chem. Int. Ed. 2009, 48. 1153-1156:
12. b) I. Prochnow, R. Kubiak, O. N. Frey, R. Beckhaus, S. Doye, ChemCatChem 2009, 1, 162-172.
13. J. A. Bexrud, P. Eisenberger, D. C. Leitch, P. R. Payne, L. L. Schafer, J. Am. Chem. Soc. 2009, 131, 2116-2118.
14. 4] as the catalyst; see Ref. [6b].
15. 2] as the catalyst, a successful hydroaminoalkylation (1-ocetene + N-methylaniline) could be achieved at a temperature of only 90°C; see Ref. [4b].
16. C. Müller, W. Saak, S. Doye, Eur. J. Org. Chem. 2008, 2731-2739.
17. For the corresponding reaction between allylbenzene and N-methylaniline, comparable yields are obtained in various solvents, such as toluene, xylenes, 1, 4-dioxane, n-heptane or diphenyl ether: N. Bruns, BSc Thesis, Universität Oldenburg, 2009.
18. A possible explanation for the fact that, among the substance class of N-alkylamines, only N-methylamines undergo successful reactions could be that a sterically more demanding N-alkyl substituent prevents alkene insertion into the carbon-titanium bond of a titanaaziridine, which is assumed to be the catalytically active species. For plausible suggestions regarding the mechanism of the hydroaminoalkylation reaction, see Refs [4-7].