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. 2009 Nov 5;11(21):4798-801.
doi: 10.1021/ol9018002.

On the impact of steric and electronic properties of ligands on gold(I)-catalyzed cycloaddition reactions

Diego Benitez  1 , Ekaterina Tkatchouk, Ana Z Gonzalez, William A Goddard 3rd, F Dean Toste
Affiliations

On the impact of steric and electronic properties of ligands on gold(I)-catalyzed cycloaddition reactions

Diego Benitez et al. Org Lett. .

Abstract

It is shown that [4 + 3] and [4 + 2] cycloaddition pathways are accessible in the Au(I) catalysis of allene-dienes. Seven-membered ring gold-stabilized carbenes, originating from the [4 + 3] cycloaddition process, are unstable and can rearrange via a 1,2-H or a 1,2-alkyl shift to yield six- and seven-membered products. Both steric and electronic properties of the AuL(+) catalyst affect the electronic structure of the intermediate gold-stabilized carbene and its subsequent reactivity.

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Figures

Figure 1
Figure 1
Calculated transition state structures (L = PMe3) for the concerted [4+2]- and [4+3]-cycloaddition reaction of dienes and gold-complexed allenes.
Figure 2
Figure 2
Calculated structures for 5, TS53 (L= P(tBu)2(o-biPh) and metal-free), and TS52 (L=P(OPh)3). Selected bond lengths for TS53 and TS52 with L= P(tBu)2(o-biPh) and L=P(OPh)3 shown in red and blue, respectively. Selected bond lengths for 5 and TS53 for metal-free structures shown in black.
Scheme 1
Scheme 1
Au-catalyzed [4+3] and [4+2]-cycloadditions.
See this image and copyright information in PMC

References

    1. Hashmi SK, Rudolph M. Chem Soc Rev. 2008;37:1766. - PubMed
    2. Gorin DJ, Sherry BD, Toste FD. Chem Rev. 2008;108:3351. - PMC - PubMed
    3. Shen HC. Tetrahedron. 2008;64:7847.
    1. Prieto A, Fructos MR, Diaz-Requejo MM, Pérez PJ, Pérez-Galán P, Delpont N, Echavarren AM. Tetrahedron. 2009;65:1790.
    2. Fürstner A, Davies PW. Angew Chem Int Ed. 2007;46:3410. - PubMed
    3. Jiménez-Núñez E, Echavarren AM. Chem Rev. 2008;108:3326. - PubMed
    4. Shapiro ND, Toste FD. J Am Chem Soc. 2007;129:4160. - PubMed
    5. Correa A, Marion N, Fensterbank L, Malacria M, Nolan SP, Cavallo L. Angew Chem, Int Ed. 2008;47:718. - PubMed
    6. Johansson MJ, Gorin DJ, Staben ST, Toste FD. J Am Chem Soc. 2005;127:18002. - PubMed
    1. Shi X, Gorin DJ, Toste FD. J Am Chem Soc. 2005;127:5802. - PubMed
    2. Fürstner A, Morency L. Angew Chem Int Ed. 2008;47:5030. - PubMed
    3. Jiménez-Núñez E, Claverie CK, Bour C, Cárdenas DJ, Echavarren AM. Angew Chem, Int Ed. 2008;47:7892. - PubMed
    4. Toullec PY, Biarre T, Michelet V. Org Lett. 2009;11:2888. - PubMed
    1. Luzung MR, Mauleón P, Toste FD. J Am Chem Soc. 2007;129:12402. - PubMed
    1. Mauleón P, Zeldin RM, Gonzalez AZ, Toste FD. J Am Chem Soc. 2009;131:6348. - PMC - PubMed

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