Ti-mediated chemoselective conversion of cyanoesters and cyanoamides into β-aminoesters and 1-aza-spirolactams bearing a cyclopropane ring

Synlett

Volumn , Issue 2, 2003, Pages 265-267

  Bertus, Philippe ^a   Szymoniak, Jan ^a  

^a UNIVERSITÉ DE REIMS CHAMPAGNE ARDENNE   (France)

Author keywords

Cyclizations; Cyclopropanes; Nitriles; Spiro compounds; Titanium

Indexed keywords

1 AZASPIROLACTAM DERIVATIVE; AMIDE; BETA AMINOESTER DERIVATIVE; CYCLOPROPANE; ESTER DERIVATIVE; TITANIUM; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL BINDING; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; CYCLOPROPANATION; STEREOCHEMISTRY; SYNTHESIS;

EID: 0037284717     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2003-36785     Document Type: Article

References (18)

1. Bertus, P.; Szymoniak, J. Chem. Commun. 2001, 1792.
2. Bertus, P.; Szymoniak, J. J. Org. Chem. 2002, 67, 3965.
3. (a) Kulinkovich, O. G.; Sviridov, S. V.; Vasilevsky, D. A.; Pritytskaja, T. S. Russ. J. Org. Chem. 1989, 25, 2027.
4. (b) Kulinkovich, O. G.; Sviridov, S. V.; Vasilevsky, D. A. Synthesis 1991, 234.
5. For reviews, see: (a) de Meijere, A.; Kozhushkov, S. I.; Savchenko, A. I. In Titanium and Zirconium in Organic Synthesis; Marek, I., Ed.; Wiley-VCH: Weinheim, 2002, 390.
6. (b) Kulinkovich, O. G.; de Meijere, A. Chem. Rev. 2000, 100, 2789.
7. Lee, J.; Kim, Y. G.; Bae, J. G.; Cha, J. K. J. Org. Chem. 1996, 61, 4878.
8. (a) Chaplinski, V.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1996, 35, 413.
9. (b) Lee, J.; Cha, J. K. J. Org. Chem. 1997, 62, 1584.
10. Carboxylic esters have been demonstrated to be generally more reactive towards the cyclopropanation reaction than the corresponding amides, see: Cho, S. Y.; Lee, J.; Lammi, R. K.; Cha, J. K. J. Org. Chem. 1997, 62, 8235.
11. 2.
12. No cyclopropane-containing product was obtained from ethyl cyanoacetate, probably due to the presence of acidic hydrogens.
13. +), 154 (18), 140 (34), 123 (60), 112 (78), 94 (100).
14. For recent reviews on the use and preparation of β-amino acids, see: (a) Steer, D. A.; Lew, R. A.; Perlmutter, P.; Smith, A. I.; Aguilar, M. I. Curr. Med. Chem. 2002, 9, 811.
15. (b) Abele, S.; Seebach, D. Eur. J. Org. Chem. 2000, 1.
16. +), 96 (48), 82 (100).
17. These spirocyclopropanelactams cannot be directly prepared from cyclic imides using the same procedure (Grignard reagent and titanium isopropoxide), since the resulting titanaoxacyclopentanes do not lead to cyclopropane formation. See: Lee, J.; Ha, J. D.; Cha, J. K. J. Am. Chem. Soc. 1997, 119, 8127.
18. The spirolactam 16, being a γ-aminobutyric acid (GABA) analogue, has already been prepared, in several steps. See: Kordes, M.; Winsel, H.; de Meijere, A. Eur. J. Org. Chem. 2000, 3235.