Highly substituted spiro[4.4]nonatrienes from a β-amino-substituted α,β-unsaturated Fischer carbene complex and three molecules of an arylalkyne

Angewandte Chemie - International Edition

Volumn 38, Issue 9, 1999, Pages 1285-1287

  Schirmer, Heiko ^a   Duetsch, Michael ^a   Stein, Frank ^a   Labahn, Thomas ^a   Knieriem, Burkhard ^a   De Meijere, Armin ^a  

^a UNIVERSITY OF GÖTTINGEN   (Germany)

Author keywords

Alkynes; Carbene complexes; Insertions; Spiro compounds

Indexed keywords

ALKYNE; SPIRO COMPOUND; SPIRO[4.4]NONATRIENE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; COMPLEX FORMATION; CRYSTAL STRUCTURE; CYCLIZATION; HEATING; MASS SPECTROMETRY; NUCLEAR MAGNETIC RESONANCE; ORGANIC CHEMISTRY; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0033519325     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19990503)38:9<1285::AID-ANIE1285>3.0.CO;2-N     Document Type: Article

References (28)

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22. T values for solvent polarity: C. Reichardt, Angew. Chem. 1979, 91, 119-131;
23. Angew. Chem. Int. Ed. Engl. 1979, 18, 98-110. The lower the solvent polarity the greater is the ratio 2:3.
24. [14] All hydrogen atoms were positioned with ideal geometries and included in the refinement. All disorders were resolved with distance and ADP restraints and anisotropically refined. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-410149. Copies of the data can be obtained free of charge by application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (Fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam. ac.uk).
25. 31NO (433.6).
26. Compound 2 yields 5-dimethylamino-3-ethoxy-1-propyl-5-trimethylsilyl-1,3-cyclopentadiene(25%)with 1-pentyne in THF after four days at 55°C, and the analogous 1,2-dimethylcyclopentadiene derivative (44%) with 2-butyne in pyridine at 80°C.
27. The possible triple insertion can be considered as the start of an alkyne polymerization catalyzed by carbene complexes which takes place by multiple insertion into the metal-carbene carbon bond. See also: T. J. Katz, S. J. Lee, J. Am. Chem. Soc. 1980, 102, 422-424. However, as one referee has commented, it has not been confirmed whether or not the products 4 and 5 are formed in a sequence of double insertion of the arylethyne, [2+1] cycloaddition of the carbene to an arylethyne, and a subsequent transformation of the thus formed hexatrienylcyclopropene. However, an appropriate mechanism is not obvious.
28. G. M. Sheldrick, SHELXL-93/97, Program for crystal structure refinement, Universität Göttingen, 1997.