Skip to main content
Log in

Rhodium complexes catalyze oxidative coupling between salicylaldehyde and phenylacetylene via C–H bond activation

  • Short Communication
  • Published:
Chemical Papers Aims and scope Submit manuscript

Abstract

A coupling reaction between salicylaldehyde and phenylacetylene was catalyzed by well-defined rhodium complexes, Rh(cod)(l-amino acid) (cod is 1,5-cyclooctadiene; l-amino acid is l-proline, l-phenylalanine and l-valine), to give a flavonoid in 40–88% yield, providing a method for flavonoid synthesis. The coupling reactions catalyzed by Rh(cod)(l-amino acid)s gave higher yields than those by [Rh(cod)Cl]2 without l-amino acid ligands. The reaction mechanism may be that l-amino acid ligands of the rhodium complexes can provide an empty track for phenylacetylene to form a ring structure that fractures to produce the aim flavonoid and RhIX species. Then, the active RhIX specie is oxidized to regenerate RhIIIX3 by Cu(OAC)2.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Scheme 2
Scheme 3

References

  • Azpíroz R, Rubio-Pérez L, Giuseppe A, Passarelli V, Lahoz F, Castarlenas R, Torrente J, Oro LA (2014) Rhodium(I)-N-heterocyclic carbene catalyst for selective coupling of N-vinylpyrazoles with alkynes via C–H activation. ACS Catal 4:4244–4253. doi:10.1021/cs501366q

    Article  Google Scholar 

  • Baker RW, Radzey H, Lucas NT, Turner P (2012) Stereospecific syntheses and structures of planar chiral Bidentateη5:κS-Indenyl-Sulfanyl and -Sulfinyl complexes of Rhodium(III). Organometallics 31:5622–5633. doi:10.1021/om300581r

    Article  CAS  Google Scholar 

  • Brasse M, Campora J, Ellman JA, Bergman RG (2013) Mechanistic study of the oxidative coupling of styrene with 2-phenylpyridine derivatives catalyzed by cationic Rhodium(III) via C–H activation. J Am Chem Soc 135:6427–6430. doi:10.1021/ja401561q

    Article  CAS  Google Scholar 

  • Fukui Y, Liu P, Liu Q, He Z, Wu NY, Tian P, Lin GQ (2014) Tunable arylative cyclization of 1,6-enynes triggered by Rhodium(III)-catalyzed C–H activation. ACS J Am Chem Soc 136:15607–15614. doi:10.1021/ja5072702

    Article  CAS  Google Scholar 

  • Huang JR, Zhang QR, Qu CH, Chen YC (2013) Rhodium(III)-catalyzed direct selective C(5)-H oxidative annulations of 2-substituted imidazoles and alkynes by double C–H activation. Org Lett. doi:10.1021/ol400537b

    Google Scholar 

  • Jia H, Teraguchi M, Aoki T, Abe Y, Kaneko T, Hadano S, Namikoshi T, Marwanta E (2009) Two modes of asymmetric polymerization of phenylacetylene having a l-valinol residue and two hydroxy groups. Macromolecules 42:17–19. doi:10.1021/ma802313z

    Article  CAS  Google Scholar 

  • Jia H, Teraguchi M, Aoki T, Abe Y, Kaneko T, Hadano S, Namikoshi T, Ohishi T (2010) Three mechanisms of asymmetric polymerization of phenylacetylenes having an l-amino ether residue and two hydroxy groups. Macromolecules 43:8353–8362. doi:10.1021/ma101424x

    Article  CAS  Google Scholar 

  • Jia H, Shi Y, Ma L, Gao X, Wang Y, Zang Y, Peng J, Aoki T, Teraguchi M, Kaneko T, Masuda T (2016) Novel isolated, l-amino acid-ligated rhodium catalysts that induce highly helix-sense-selective polymerization of an achiral 3,4,5-trisubstituted phenylacetylene. J Poym Sci Part A 54:2346–2351. doi:10.1002/pola.28106

    Article  CAS  Google Scholar 

  • Jin Y, Kim H, Kim J, Heo N, Shin J, Teraguchi M, Kaneko T, Aoki T, Kwak G (2016) Asymmetric restriction of intramolecular rotation in chiral solvents. Cryst Growth Des 2016(16):2804–2809. doi:10.1021/acs.cgd.6b00128

    Article  Google Scholar 

  • Kaneko T, Abe H, Teraguchi M, Aoki T (2013) Folding-induced through-space magnetic interaction of poly(1,3-phenyleneethynylene)-based polyradicals. Macromolecules 2013(46):2583–2589. doi:10.1021/ma302314n

    Article  Google Scholar 

  • Kim H, Seo K, Jin Y, Lee C, Teraguchi M, Kaneko T, Aoki T, Kwak G (2016) Highly emissive, optically active poly(diphenylacetylene) having a bulky chiral side group. ACS Macro Lett 5:622–625. doi:10.1021/acsmacrolett.6b00184

    Article  CAS  Google Scholar 

  • Kokubo K, Matsumasa K, Miura M, Nomura M (1997) Rhodium-catalyzed coupling reaction of salicyl aldehydes with alkynes via cleavage of the aldehyde C–H bond. J Org Chem 62:4564–4565

    Article  CAS  Google Scholar 

  • Kokubo K, Matsumasa K, Nishinaka Y, Miura M, Nomura M (1999) Reaction of 2-hydroxybenzaldehydes with alkynes, alkenes, or allenes via cleavage of the aldehyde C–H bond using a rhodium catalyst system. Bull Chem Soc Jpn 72:303–311

    Article  CAS  Google Scholar 

  • Liu L, Zang Y, Hadano S, Aoki T, Teraguchi M, Kaneko T, Namikoshi T (2010) New achiral phenylacetylene monomers having an oligosiloxanyl group most suitable for helix-sense-selective polymerization and for obtaining good optical resolution membrane materials. Macromolecules 43:9268–9276. doi:10.1021/ma101999k

    Article  CAS  Google Scholar 

  • Liu L, Namikoshi T, Zang Y, Aoki T, Hadano S, Abe Y, Wasuzu I, Tsutsuba T, Teraguchi M, Kaneko T (2013) Top-down preparation of self-supporting supramolecular polymeric membranes using highly selective photocyclic aromatization of cis−cisoid helical poly(phenylacetylene)s in the membrane state. J Am Chem Soc 135:602–605. doi:10.1021/ja3113214

    Article  CAS  Google Scholar 

  • Luo C, Gandeepan P, Wu Y, Tsai C, Cheng C (2015a) Cooperative C(sp3)−H and C(sp2)−H activation of 2-ethylpyridines by copper and rhodium: a route toward quinolizinium salts. ACS Catal 5:4837–4841. doi:10.1021/acscatal.5b01244

    Article  CAS  Google Scholar 

  • Luo C, Jayakumar J, Gandeepan P, Wu Y, Cheng C (2015b) Rhodium(III)-catalyzed vinylic C−H activation: a direct route toward pyridinium salts. Org Lett 17:924–927. doi:10.1021/acs.orglett.5b00028

    Article  CAS  Google Scholar 

  • Nishimura T, Takiguchi Y, Hayashi T (2012) Effect of chiral diene ligands in rhodium-catalyzed asymmetric addition of arylboronic acids to α, β-unsaturated sulfonyl compounds. ACS J Am Chem Soc 134:9086–9089. doi:10.1021/ja303109q

    Article  CAS  Google Scholar 

  • Riener K, Hogerl MP, Gigler P, Kuhn FE (2012) Rhodium-catalyzed hydrosilylation of ketones: catalyst development and mechanistic insights. ACS Catal 2:613–621. doi:10.1021/cs200571v

    Article  CAS  Google Scholar 

  • Sahoo S, Banerjee A, Chakraborty S, Patel B (2012) Regioselective intramolecular arylthiolations by ligand free Cu and Pd catalyzed reaction. ACS Catal 2:544–551. doi:10.1021/cs200590p

    Article  CAS  Google Scholar 

  • Shimizu M, Tsurugi H, Satoh T, Miura M (2008) Rhodium-catalyzed oxidative coupling between salicylaldehydes and internal alkynes with C–H bond cleavage to produce 2,3-disubstituted chromones. Chem Asian J 3:881–886. doi:10.1002/asia.200800037

    Article  CAS  Google Scholar 

  • Staubitz A, Robertson APM, Sloan ME, Manners I (2015) Amine- and phosphine-borane adducts: new interest in old molecules. Chem Rev 110:4023–4078. doi:10.1021/cr100105a

    Article  Google Scholar 

  • Teraguchi M, Tanioka D, Kaneko T, Aoki T (2010) Helix-sense-selective polymerization of achiral phenylacetylenes with two N-alkylamide groups to generate the one-handed helical polymers stabilized by intramolecular hydrogen bonds. ACS Macro Lett 1:1258–1261. doi:10.1021/mz300309c

    Article  Google Scholar 

  • Youn SW, Bihn JH, Kim BS (2011) Pd-catalyzed intramolecular oxidative C–H amination: synthesis of carbazoles. Org Lett 13:3738–3741. doi:10.1021/ol201416u

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (U1162123) and (51103076), the Natural Science Foundation of Heilongjiang Province of China (LC2011C12), the Overseas Scholars Foundation of the Education Department of Heilongjiang Province of China (1251H012) and the New Century Excellent Talents of the Education Department of Heilongjiang Province of China (1253-NCET-24).

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Hongge Jia, Yanan Tang or Liqun Ma.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 732 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Jia, H., Tang, Y., Shi, Y. et al. Rhodium complexes catalyze oxidative coupling between salicylaldehyde and phenylacetylene via C–H bond activation. Chem. Pap. 71, 1791–1795 (2017). https://doi.org/10.1007/s11696-017-0153-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11696-017-0153-4

Keywords

Navigation