A straightforward and mild synthesis of functionalized 3-alkynoates

Angewandte Chemie - International Edition

Volumn 43, Issue 27, 2004, Pages 3580-3582

  Suárez, Andrés ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

Alkynes; Copper; Diazo compounds; Homogeneous catalysis

Indexed keywords

CHEMICAL BONDS; COPPER COMPOUNDS; SYNTHESIS (CHEMICAL); THERMAL EFFECTS;

COUPLING REACTIONS; DIAZOACETATES;

AROMATIC COMPOUNDS;

ACETIC ACID DERIVATIVE; ALKYNE DERIVATIVE; COPPER DERIVATIVE; HYDROXYL GROUP; IODINE; LIGAND;

ARTICLE; ATOM; CATALYST; CHEMICAL BOND; ROOM TEMPERATURE; SYNTHESIS;

EID: 4544224672     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200454070     Document Type: Article

References (20)

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14. The observed solvent effects may be due in part to the relative solubility of CuI.
15. For a discussion of this problem, see p. 6 of: T. Rovis, D. A. Evans, Prog. Inorg. Chem. 2001, 50, 1-150. The typical remedy is to use a large excess of the substrate (e.g., as the solvent) and to employ slow addition of the diazo compound.
16. The 3-alkynoate:allene ratio does not change as the reaction progresses, which suggests that the 3-alkynoate is not an intermediate in the formation of the allene.
17. The isomeric allene is the only identifiable side product.
18. For an early example, see: G. Pourcelot, L. Veniard, P. Cadiot, Bull. Soc. Chim. Fr. 1975, 1281-1283. See also reference [3], Chapter 7.
19. This result is particularly noteworthy in light of a recent report of selective O-H insertion upon reacting propargyl alcohol with ethyl diazoacetate in the presence of a CuTp catalyst (Tp = a homoscorpionate ligand): M. E. Morilla, M. J. Molina, M. M. Díaz-Requejo, T. R. Belderrain, M. C. Nicasio, S. Trofimenko, P. J. Pérez, Organometallics 2003, 22, 2914-2918.
20. We have not optimized the reaction conditions for the reactions in Table 3; they are the same as those used for the reactions in Table 2.