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Organic & Biomolecular Chemistry
Page 4 of 5
DOI: 10.1039/C7OB02397A
COMMUNICATION
Journal Name
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Scheme
5
Stereocontrolled synthesis of tetrahydrothiophens
1
via Brønsted-base-
catalyzed remote functionalization of 2,4-dienones 2 – mechanistic consideration
In conclusion, we have demonstrated that the remote
functionalization of 2,4-dienones can be accomplished
employing organocatalytic Brønsted base activation mode. As
Boratyński, A. J. Wierzba and J. Bąkowicz, RSC Adv., 2015,
66681; k) X. Sun, J. Fei, C. Zou, M. Lu and Jinxing Ye, RSC
Adv., 2016, , 106676.
5,
a
result
a
facile approach to optically active
6
tetrahydrothiophenes bearing three contiguous stereocenters
including one quaternary has been developed. Notably, simple
and readily available cinchonine was used to promote the
reaction cascade involving 1,6-addition followed by the
intramolecular aldol reaction. The developed cascade
reactivity benefits from the broad scope and excellent stereo-
and regiocontrol affording only one of the possible products.
9
L. Bernardi, J. Llpez-Cantarero, B. Niess and K. A. Jørgensen,
J. Am. Chem. Soc., 2007, 129, 5772.
10 There is only one report covering thia-Michael/aldol cascade
represented by single reaction of (2E,4E)-1,5-diphenylpenta-
2,4-dien-1-one with 1,4-dithiane-2,5-diol catalyzed by chiral
squaramide: J.-B. Ling, Y. Su, H.-L. Zhu, G.-Y. Wang and P.-F.
Xu, Org. Lett., 2012, 14, 1090.
11 For a general review, see: a) T. Marcelli and H. Hiemstra,
Synthesis, 2010, 8, 1229; for the application of simple
alkaloids in the thia-Michael reaction of (2E,4E)-6-oxo-2,4-
dienoates, see: b) R. Kowalczyk, A. J. Wierzba, P. J. Boratyński
and J. Bąkowicz, Tetrahedron, 2014, 70, 5834.
This project was realized within the Sonata Bis programme
(grant number: 2015/18/E/ST5/00309) from the National
Science Centre, Poland. Thanks are expressed to Dr. Jakub
Wojciechowski (Faculty of Chemistry, Lodz University of
Technology) for performing X-ray analysis.
12 For a discussion of electronic character of the π-systems
studied here, see ref. 8g and D. Duvvuru, J.-F. Betzer, P.
Retailleau, G. Frison and A. Marinetti, Adv. Synth. Catal.,
2011, 353, 483.
13 CCDC 1548930 contains the supplementary crystallographic
data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
Notes and references
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4 | Org. Biomol. Chem., 2017, 00, 1-3
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