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DOI: 10.1055/s-0028-1083165
gem-Dimethylcyclopropanation Using Triisopropylsulfoxonium Tetrafluoroborate: Scope and Limitations
Publication History
Publication Date:
25 September 2008 (online)
Abstract
A new nucleophilic isopropyl transfer reagent, triisopropylsulfoxonium tetrafluoroborate, has been prepared and evaluated. Thus, using this reagent and NaH in DMF, a range of electron deficient alkenes, including several chalcone analogues, α,β-unsaturated ketones, dienones and quinones, plus α,β-unsaturated esters, nitrile, sulfone and nitro examples, have been converted into the corresponding gem-dimethylcyclopropane compounds.
Key words
cyclopropanes - cyclopropanation - sulfoxonium salts - ruthenium tetraoxide
- 1
Simmons HE.Smith RD. J. Am. Chem. Soc. 1959, 81: 4256 - 2
Kostikov RR.Molchanov AP.Khlebnikov AF. Russ. Chem. Rev. 1989, 58: 654 -
3a
Corey EJ.Chaykovsky M. J. Am. Chem. Soc. 1962, 84: 867 -
3b
Corey EJ.Chaykovsky M. J. Am. Chem. Soc. 1962, 84: 3782 -
3c
Corey EJ.Chaykovsky M. J. Am. Chem. Soc. 1965, 87: 1353 -
3d
Yanovskaya LA.Dombrovsky VA.Chizhov OS.Zolotarev BM.Subbotin OA.Kucherov VF. Tetrahedron 1972, 28: 1565 - 4 For a review, see:
Aggarwal VK.Li A.-H.Dai L.-X. Chem. Rev. 1997, 97: 2341 - For recent asymmetric examples, see:
-
5a
Papageorgiou CD.Cubillo de Dios MA.Ley SV.Gaunt MJ. Angew. Chem. Int. Ed. 2004, 43: 4641 -
5b
Kunz RK.MacMillan DWC. J. Am. Chem. Soc. 2005, 127: 3240 -
6a
Oswald MF.Raw SA.Taylor RJK. Org. Lett. 2004, 6: 3997 -
6b
Oswald MF.Raw SA.Taylor RJK. Chem. Commun. 2005, 2253 -
6c
McAllister GD.Oswald MF.Paxton RJ.Raw SA.Taylor RJK. Tetrahedron 2006, 62: 6681 - 7
Paxton RJ.Taylor RJK. Synlett 2007, 633 - 8
Hossain MM.Suzuki T.Sato I.Takewaki T.Suzuki K.Kobayashi H. Life Sci. 2005, 77: 795 ; and references cited therein - 9
von Reuss SH.Wu C.-L.Muhle H.Konig WA. Phytochemistry 2004, 65: 2277 ; and references cited therein - 10
Gao S.Liu H.-Y.Wang Y.-H.He H.-P.Wang J.-S.Di Y.-T.Li C.-S.Fang X.Hao X.-J. Org. Lett. 2007, 9: 3453 -
11a
Corey EJ.Posner GH. J. Am. Chem. Soc. 1967, 89: 3911 -
11b
Franck-Neumann M. Angew. Chem., Int. Ed. Engl. 1968, 7: 65 -
11c
Sengmany S.Léonel E.Paugam JP.Nédélec J.-Y. Tetrahedron 2002, 58: 271 -
11d
Charette AB.Wilb N. Synlett 2002, 176 ; and references cited therein -
12a
Corey EJ.Jautelat M. J. Am. Chem. Soc. 1967, 89: 3912 -
12b
Corey EJ.Jautelat M.Oppolzer W. Tetrahedron Lett. 1967, 8: 2325 -
12c
Tang CSF.Rapoport H. J. Org. Chem. 1973, 38: 2806 -
12d For an asymmetric variant,
see:
Mamai A.Madalengoitia JS. Tetrahedron Lett. 2000, 41: 9009 - 13
Johnson CR.Janiga ER. J. Am. Chem. Soc. 1973, 95: 7692 -
14a
Devos MJ.Krief A. Tetrahedron Lett. 1979, 20: 1515 -
14b
Krief A.Dubois P. Tetrahedron Lett. 1993, 34: 2691 - 15
Ono N.Yanai T.Hamamoto I.Kamimura A.Kaji A. J. Org. Chem. 1985, 50: 2806 - 16
Mori M.Takeuchi H.Minato H.Kobayashi M.Yoshida M.Matsuyama H.Kamigata N. Phosphorus, Sulfur Silicon Relat. Elem. 1990, 47: 157 -
17a
Martín VS.Palazón JM.Rodríguez CM.Nevill CR. In Encyclopedia of Reagents for Organic SynthesisPaquette LA. Wiley; New York: 2004. -
17b For its use in the preparation
of a sulfoxonium salt, see:
Forrester J.Jones RVH.Preston PN.Simpson ESC. J. Chem. Soc., Perkin Trans. 1 1995, 2289 -
18a
Djerassi C.Engle RR. J. Am. Chem. Soc. 1953, 75: 3838 -
18b
Berkowitz LM.Rylander PN. J. Am. Chem. Soc. 1958, 80: 6682 - 19 Preliminary communication:
Edwards MG.Paxton RJ.Pugh DS.Taylor RJK. Synlett 2008, 521 - See, for example:
-
20a
Major RT.Hess H.-J. J. Org. Chem. 1958, 23: 1563 -
20b
Kobayashi M.Kamiyama K.Minato H.Oishi Y.Takada Y.Hattori Y. Bull. Chem. Soc. Jpn. 1972, 45: 3703 - 21
Badet B.Julia M. Tetrahedron Lett. 1979, 20: 1101 - 22
Kishi Y.Aratani M.Tanino H.Fukuyama T.Goto T.Inoue S.Sugiura S.Kakoi H. J. Chem. Soc., Chem Commun. 1972, 64 - 23
Carlsen PHJ.Katsuki T.Martin VS.Sharpless KB. J. Org. Chem. 1981, 46: 3936 - 24
Lui K.-H.Sammes MP. J. Chem. Soc., Perkin Trans. 1 1990, 457 -
25a
Noyce DS.Pryor WA.King PA. J. Am. Chem. Soc. 1959, 81: 5423 -
25b
For the hydrogenation of the corresponding alkyne we employed 5% Pd on BaSO4 and 30% quinoline in EtOAc (3 h).
- 26
Armesto D.Ortiz MJ.Agarrabeitia AR.Martín-Fontecha M. Org. Lett. 2005, 7: 2687 - 27
Ceccherelli P.Curini M.Marcotullio MC.Rosati O. Tetrahedron 1992, 44: 9767 - 29
Kohmoto S.Kasimura H.Nishio T.Iida I.Kishikawa K.Yamamoto M.Yamada K. J. Chem. Soc., Perkin Trans. 2 1994, 1565
References
CCDC-687178 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 (1223)336033; E-mail: admin@ccdc.cam.ac.uk].