Volume 43, Issue 27 pp. 3580-3582

Communication

A Straightforward and Mild Synthesis of Functionalized 3-Alkynoates^†

Andrés Suárez Dr.,

Andrés Suárez Dr.

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA, Fax: (+1) 617-324-3611

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Gregory C. Fu Prof. Dr.,

Gregory C. Fu Prof. Dr.

[email protected]

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA, Fax: (+1) 617-324-3611

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Andrés Suárez Dr.,

Andrés Suárez Dr.

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA, Fax: (+1) 617-324-3611

Search for more papers by this author

Gregory C. Fu Prof. Dr.,

Gregory C. Fu Prof. Dr.

[email protected]

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA, Fax: (+1) 617-324-3611

Search for more papers by this author

First published: 29 June 2004

https://doi.org/10.1002/anie.200454070

Citations: 152

^†

Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, R01-GM066960), the Spanish Ministry of Education, Culture, and Sports (postdoctoral fellowship to A.S.), Merck Research Laboratories, and Novartis. Funding for the MIT Department of Chemistry Instrumentation Facility has been furnished in part by NSF CHE-9808061 and NSF DBI-9729592.

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Graphical Abstract

Diazoacetates in coupling reactions: CuI serves as an effective catalyst for coupling terminal alkynes with diazo compounds to generate 3-alkynoates (see scheme). This method is efficient (1:1 ratio of reactants), mild (room temperature), and simple (no additional ligand), and a range of functional groups are tolerated (e.g., CC double bonds, heteroatoms, and hydroxy groups).

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References

1For some examples, see:
Google Scholar
1aS.-i. Usugi, H. Yorimitsu, H. Shinokubo, K. Oshima, Bull. Chem. Soc. Jpn. 2002, 75, 2687–2690;
10.1246/bcsj.75.2687
CAS Web of Science® Google Scholar
1bR. M. Williams, D. J. Aldous, S. C. Aldous, J. Org. Chem. 1990, 55, 4657–4663;
10.1021/jo00302a034
CAS Web of Science® Google Scholar
1cJ. Hooz, R. B. Layton, Can. J. Chem. 1972, 50, 1105–1107.
10.1139/v72-175
CAS Web of Science® Google Scholar
2For a discussion, see: O. M. Nefedov, E. A. Shapiro, A. B. Dyatkin in Supplement B: The Chemistry of Acid Derivatives, Vol. 2 (Ed.: ) Wiley, New York, 1992, pp. 1527–1528.
Google Scholar
3M. P. Doyle, M. A. McKervey, T. Ye in Modern Catalytic Methods for Organic Synthesis with Diazo Compounds, Wiley, New York, 1998.
Google Scholar
4For leading references, see:
Google Scholar
4areference [3], Chapter 4.11;
Google Scholar
4bM. N. Protopopova, E. A. Shapiro, Russ. Chem. Rev. 1989, 58, 667–681.
10.1070/RC1989v058n07ABEH003469
Google Scholar
5For a discussion and leading references, see: M. M. Díaz-Requejo, M. A. Mairena, T. R. Belderrain, M. C. Nicasio, S. Trofimenko, P. J. Pérez, Chem. Commun. 2001, 1804–1805.
10.1039/b105020f
PubMed Web of Science® Google Scholar
6
6aV. E. Baikov, L. P. Danilkina, K. A. Ogloblin, Russ. J. Gen. Chem. 1983, 53, 2172–2173;
Google Scholar
6bE. A. Shapiro, I. E. Dolgii, O. M. Nefedov, Bull. Acad. Sci. USSR Div. Chem. Sci. (Engl. Transl.) 1980, 29, 1493–1499;
10.1007/BF01168281
Web of Science® Google Scholar
6cI. E. Dolgii, E. A. Shapiro, O. M. Nefedov, Bull. Acad. Sci. USSR Div. Chem. Sci. (Engl. Transl.) 1974, 23, 929;
10.1007/BF00923549
Google Scholar
6dM. Vidal, M. Vincens, P. Arnaud, Bull. Soc. Chim. Fr. 1972, 657–665;
CAS Web of Science® Google Scholar
6eV. K. Jones, A. J. Deutschman Jr., J. Org. Chem. 1965, 30, 3978–3980.
10.1021/jo01022a529
CAS Web of Science® Google Scholar
7The observed solvent effects may be due in part to the relative solubility of CuI.
Google Scholar
8For 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.
10.1002/0471227110.ch1
CAS Web of Science® Google Scholar
9The 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.
Google Scholar
10The isomeric allene is the only identifiable side product.
Google Scholar
11For an early example, see: G. Pourcelot, L. Veniard, P. Cadiot, Bull. Soc. Chim. Fr. 1975, 1281–1283. See also reference [3], Chapter 7.
CAS Web of Science® Google Scholar
12This 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.
10.1021/om030243a
CAS Web of Science® Google Scholar
13We 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.
Google Scholar

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Volume43, Issue27

July 5, 2004

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A Straightforward and Mild Synthesis of Functionalized 3-Alkynoates^†

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A Straightforward and Mild Synthesis of Functionalized 3-Alkynoates^†