Organic Letters
Letter
phenyl sulfoxide, the precursor of MPS,12 authenticates the
transformable (Tf)-DG nature of the MPS moiety.
(3) (a) Yadav, M. R.; Rit, R. K.; Shankar, M.; Sahoo, A. K. J. Org.
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The one-pot double annulation is comprised of the
cyclizations of acrylamide with two alkynes.16 The complete
reaction could involve the chelation of the MPS-N moiety with
the cationic Ru complex,4b formation of a five membered
ruthenacycle via β-C−H activation of acrylamide, alkyne
insertion to the ruthenacycle, migratory insertion, and
cyclization with concomitant release of methyl phenylsulfoxide
generating another 5-membered ruthenacycle via the coordi-
nation of pyridone−N-Ru−proximal-o-C−H-aryl, which would
eventually undergo an annulation with the alkyne to give the
desired double cyclization product.16,19 The acetate source of
Cu(OAc)2·H2O presumably helps the formation of active
catalyst and also behaves as oxidant in the second
annulation.4,19
In conclusion, we developed a novel transformable
sulfoximine DG-assisted oxidative double annulation of acrylic
and 2H-chromene-3-carboxylic acid derivatives with unacti-
vated alkynes under Ru catalysis. This transformation can be
used to construct four bonds (two C−C and two C−N) in a
naked acrylamide in a single operation and can be used to
produce a wide range of complex π-extended polycyclic amides
with good functional group tolerance in good yields. The
challenging unsymmetrical double annulation of acrylamides
with two distinct alkynes is also demonstrated.
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(13) The DG-assisted Ru-mediated activation of the C−H bond
occurs at room temperature, and the release of sulfoxide from the
sterically encumbered metallacycle RuL-MPS moiety (Int-II; see the
SI) and the direct participation of Int-IV (see the SI) presumably helps
the annulation.
(14) CCDC 1572523 (3ae) and 1572524 (3aj) contains the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from the Cambridge Crystallographic Data
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
Detailed experimental procedures, NMR spectra, and X-
ray crystallographic data (PDF)
X-ray data for compound 3ae (CIF)
X-ray data for compound 3aj (CIF)
AUTHOR INFORMATION
Corresponding Author
■
ORCID
Notes
The authors declare no competing financial interest.
(15) The isolation of unreacted monocyclization product and starting
material satisfies the mass balance of the reaction.
(17) Nicolaou, K. C.; Pfefferkorn, J. A.; Roecker, A. J.; Cao, G.-Q.;
Barluenga, S.; Mitchell, H. J. J. Am. Chem. Soc. 2000, 122, 9939.
(18) The reaction of 2a with unsymmetrical diarylalkynes provided a
mixture of annulated products, leading to a tedious and unsuccessful
purification.
ACKNOWLEDGMENTS
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We thank SERB (EMR/2014/385) for financial support and
University of Hyderabad (UoH; UPE-CAS and PURSE-FIST)
for overall facility. M.S. and E.R. thank CSIR, and T.R.G. (N-
PDF; DST), India, for fellowships. Dr. K. Nagarjuna (UoH) is
thanked for the crystallographic studies.
(19) Li, B.; Feng, H.; Wang, N.; Ma, J.; Song, H.; Xu, S.; Wang, B.
Chem. - Eur. J. 2012, 18, 12873.
REFERENCES
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