Specific synthesis of 1,2- and 1,3-dialkylidenecycloheptanes by [3+2+2] cyclization of alkenyl Fischer carbene complexes and allenes

Journal of the American Chemical Society

Volumn 126, Issue 44, 2004, Pages 14354-14355

  Barluenga, Jośe ^a   Vicente, Rubén ^a   Barrio, Pablo ^a   Loṕez, Luis A ^a   Tomás, Miguel ^a   Borge, Javier ^a  

^a UNIVERSITY OF OVIEDO   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ACETONITRILE; ALKENYL GROUP; ALKYL GROUP; ALLENE DERIVATIVE; CARBENOID; COORDINATION COMPOUND; CYCLOHEPTANE DERIVATIVE; NICKEL; RHODIUM;

ARTICLE; CATALYST; CHEMICAL BOND; CHEMICAL INTERACTION; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; DIASTEREOISOMER; ELIMINATION REACTION; ISOMERIZATION; NUCLEAR OVERHAUSER EFFECT; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; REDUCTION; ROOM TEMPERATURE; STEREOCHEMISTRY; STRUCTURE ANALYSIS; SYNTHESIS; TECHNIQUE; TEMPERATURE DEPENDENCE; THERMODYNAMICS; THERMOSTABILITY;

EID: 7744232980     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja045459y     Document Type: Article

References (25)

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17. Compounds 4-6 were characterized by NMR techniques (including HMQC, HMBC, COSY, and NOESY).
18. 8 above 80 °C in the NMR
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22. It is well stablished that the metal reductive elimination is retarded by σ-donor ligands and facilitated by cationic metal complexes: Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; University Science Books: Mill Valley, CA, 1987.
23. In the case of cationic rhodium(1) catalyst, the intermediate of type IV undergoes metal elimination faster than equilibration to intermediate of type V (ref 6d). Conversely, when the reaction with neutral Rh(I) catalyst is effected in the presence of a good π-acceptor ligand which favors the metal elimination (ref 11), e.g. CO, the process actually results in the clean formation of cyclopentene 7 (88% yield).
24. Regarding the 1,3-dialkylidenecycloheptane ring, a SciFinder search reveals that only the 2,7-dialkylidenecycloheptanone skeleton is known.
25. One reviewer has pointed that a product-driven argument (Ni π-allyl species II vs Rh vinyl species IV/V) can be taken into consideration.