Synlett 2014; 25(08): 1155-1159
DOI: 10.1055/s-0033-1341046
letter
© Georg Thieme Verlag Stuttgart · New York

Rhodium(I)-Catalyzed Carbonylative Arylation of Alkynes with Arylboronic Acids Using Formaldehyde as a Carbonyl Source

Chuang Wang
a   Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192, Japan   Fax: +81(743)726081   Email: morimoto@ms.naist.jp
,
Tsumoru Morimoto*
a   Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192, Japan   Fax: +81(743)726081   Email: morimoto@ms.naist.jp
,
Hiroyuki Kanashiro
a   Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192, Japan   Fax: +81(743)726081   Email: morimoto@ms.naist.jp
,
Hiroki Tanimoto
a   Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192, Japan   Fax: +81(743)726081   Email: morimoto@ms.naist.jp
,
Yasuhiro Nishiyama
a   Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192, Japan   Fax: +81(743)726081   Email: morimoto@ms.naist.jp
,
Kiyomi Kakiuchi
a   Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192, Japan   Fax: +81(743)726081   Email: morimoto@ms.naist.jp
,
Levent Artok
b   Department of Chemistry, Faculty of Science, Izmir Institute of Technology, Urla 35430, Izmir, Turkey
› Author Affiliations
Further Information

Publication History

Received: 27 January 2014

Accepted after revision: 28 February 2014

Publication Date:
27 March 2014 (online)


Abstract

The rhodium(I)-catalyzed reaction of alkynes with arylboronic acids in the presence of formaldehyde resulted in a carbon monoxide gas-free carbonylative arylation to yield α,β-enones. The simultaneous loading of phosphine-ligated and phosphine-free rhodium(I) complexes is required for efficient catalysis, which catalyze the abstraction of a carbonyl moiety from formaldehyde (decarbonylation) and its subsequent introduction into the substrate (carbonylation), respectively.

Supporting Information

 
  • References and Notes

  • 2 For a review, see: Morimoto T, Kakiuchi K. Angew. Chem. Int. Ed. 2004; 43: 5580

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  • 8 Abbreviations: BIPHEP = 2,2′-bis(diphenylphosphino)-1,1′-biphenyl; Xantphos = 9,9-dimethyl-4,5-bis(diphenyl-phosphino)xanthene; dppe = 1,2-bis(diphenylphosphino)-ethane; dppp = 1,3-bis(diphenylphosphino)propane; dppf = 1,1′-bis(diphenylphosphino)ferrocene; BINAP = 2,2′ = bis(diphenylphosphino)-1,1′-binaphthyl.
    • 9a Fristrup P, Kreis M, Palmelund A, Norrby P.-O, Madsen R. J. Am. Chem. Soc. 2008; 130: 5206
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  • 10 The role of TFA is, at present, unclear. We postulate the following two possibilities: (i) it promotes the generation of free formaldehyde from paraformaldehyde, and (ii) it accelerates the protonation of the vinylrhodium species E to give the product.

    • The fact that the deuteration of the β-position of the enones 3aa does not reach 99% is due to H–D exchange via 1,3- and 1,4-shift of the rhodium in the intermediate E to other Ph rings at β-position:
    • 11a Sasaki K, Nishimura T, Shintani R, Kantchev EA. B, Hayashi T. Chem. Sci. 2012; 3: 1278
    • 11b Hayashi T, Inoue K, Taniguchi N, Ogasawara M. J. Am. Chem. Soc. 2001; 123: 9918 ; indeed, the H integration of the aromatic ring is lower than that of 3aa from the reaction of 1a with PhB(OH)2 using (CH2O)n
  • 12 Even when C6F5CHO, which should not generate a RhH species, was used as a carbonyl source, the reaction gave unselectively a mixture of (E)- and (Z)-3aa in 2% yield (E/Z = 37:63). We have observed the similar result when carbon monoxide was used as a carbonyl source (ref. 7).
  • 13 Each of the (E)- and (Z)-3aa isolated in pure form was introduced into reactions of 4-methoxyphenylboronic acid (2b) and alkyne 1a under the standard conditions. Each reaction gave the product 3ab in almost the same yield. It is noteworthy that 3aa was recovered in the same E/Z ratio (E/Z = 32:68) in each case and that they are also the same as that of the reaction in Table 1, entry 2. Thus, E/Z isomerization of the products 3 takes place readily under the present conditions. Moreover, the reactions of (E)- and (Z)-3aa in the presence of a catalytic amount of RhH(CO)(PPh3)3 gave a E/Z mixture of 3aa quantitatively in a similar ratio, E/Z = 36:64 and 34:66, respectively. Therefore, we currently do not eliminate the possibility that E/Z isomerization proceeds via the hydrorhodation of RhH, generated from Rh and hydrogen (decarbonylation counterpart), to the primary product (E)-enone and the subsequent rotation of the C–C single bond, followed by the β-H elimination to (Z)-enone. See the Supporting Information.