RSS-Feed abonnieren
DOI: 10.1055/s-0029-1219823
Benzylic and Allylic Oxidations with Bis(trifluoroacetoxyiodo)benzene and tert-Butyl Hydroperoxide
Publikationsverlauf
Publikationsdatum:
15. April 2010 (online)
![](https://www.thieme-connect.de/media/synlett/201009/lookinside/thumbnails/10.1055-s-0029-1219823-1.jpg)
Abstract
Oxidation of benzylic and allylic substrates with a bis(trifluoroacetoxyiodo)benzene/tert-butyl hydroperoxide system to the corresponding α,β-unsaturated enones was investigated. The scope and reaction mechanism are discussed.
Key words
hydrocarbons - hypervalent iodine - tert-butyl hydroperoxide - radical reaction - oxidation - ketones
-
1a
Hypervalent
Iodine Chemistry: Modern Developments in Organic Synthesis
Wirth T. Topics in Current Chemistry Series 224, Springer; Berlin/Tokyo: 2003. -
1b
Varvoglis A. The Organic Chemistry of Polycoordinated Iodine VCH Publishers; New York: 1992. -
1c
Varvoglis A. Hypervalent Iodine in Organic Synthesis Academic Press; London: 1997. -
1d
Moriarty RM.Prakash O. Hypervalent Iodine in Organic Chemistry: Chemical Transformations Wiley-Interscience; Chichester: 2008. -
1e
Stang PJ.Zhdankin VV. Chem. Rev. 1996, 96: 1123 -
1f
Zhdankin VV.Stang PJ. Chem. Rev. 2002, 102: 2523 -
1g
Wirth T.Hirt UH. Synthesis 1999, 1271 -
1h
Stang PJ. J. Org. Chem. 2003, 68: 2997 -
1i
Moriarty RM. J. Org. Chem. 2005, 70: 2893 -
1j
Wirth T. Angew. Chem. Int. Ed. 2005, 44: 3656 -
1k
Varvoglis A. Tetrahedron 1997, 53: 1179 -
1l
Zhdankin VV.Stang PJ. Chem. Rev. 2008, 108: 5299 - 2
Milas NA.Plesnicar B. J. Am. Chem. Soc. 1968, 90: 4450 -
3a
Plesnicar B.Russell GA. Angew. Chem., Int. Ed. Engl. 1970, 9: 797 -
3b
Plesnicar B. J. Org. Chem. 1975, 40: 3267 -
4a
Ochiai M.Ito T.Masaki Y.Shiro M. J. Am. Chem. Soc. 1992, 114: 6269 -
4b
Ochiai M.Ito T.Takahashi H.Nakanishi A.Toyonari M.Sueda T.Goto S.Shiro M. J. Am. Chem. Soc. 1996, 118: 7716 -
5a
Traylor TG.Xu F. J. Am. Chem. Soc. 1987, 109: 6201 -
5b
Traylor TG.Fann W.-P.Bandyopadhyay D.
J. Am. Chem. Soc. 1989, 110: 8009 -
5c
Ochiai M.Nakanishi A.Ito T. J. Org. Chem. 1997, 62: 4253 -
5d
Ochiai M.Kajishima D.Sueda T. Heterocycles 1997, 46: 71 -
5e
Ochiai M.Kajishima D.Sueda T. Tetrahedron Lett. 1999, 40: 5541 -
5f
Ochiai M.Nakanishi A.Yamada A. Tetrahedron Lett. 1997, 38: 3927 -
5g
Hypervalent Iodine
Chemistry: Reactivites, Properties, Structures
Topics
in Current Chemistry Series 224:
Ochiai M. Springer; Berlin / Heidelberg: 2003. -
5h
Sueda T.Takeuchi Y.Suefuji T.Ochiai M. Molecules 2005, 10: 195 -
5i
Catino AJ.Nichols JM.Forslund RE.Doyle MP. Org. Lett. 2005, 7: 263 -
5j
Catino AJ.Nichols JM.Forslund RE.Doyle MP. Org. Lett. 2005, 7: 2787 -
5k
Nicolaou KC.Baran PS.Zhong Y.-L. J. Am. Chem. Soc. 2001, 123: 3183 -
5l
Dohi T.Takenaga N.Goto A.Fujioka H.Kita Y. J. Org. Chem. 2008, 73: 7365 -
6a
Catir M.Kilic H. Synlett 2003, 1180 -
6b
Catir M.Kilic H. Synlett 2004, 2151 -
7a
Bonvin Y.Callens E.Larrosa I.Henderson DA.Oldham J.Burton AJ.Barrett AGM. Org. Lett. 2005, 7: 4549 -
7b
Shaabani A.Soleimani K.Bazgir A. Synth. Commun. 2004, 34: 3303 -
9a
Silvestre SM.Salvador JAR. Tetrahedron 2007, 63: 2439 -
9b
Fang X.-Q.Xu H.-J.Jiang H.Liu Y.-C.Fu Y.Wu Y.-D. Tetrahedron Lett. 2009, 50: 312 - 10
Bellale EV.Bhalerao DS.Akamanchi KG. J. Org. Chem. 2008, 73: 9473 - 11
Suman LJ.Vishal BS.Bir S. Tetrahedron 2006, 62: 6841 - 12
Dilling WL.Plepys RA. J. Org. Chem. 1970, 35: 2971 -
13a
Rothman ES.Day AR. J. Am. Chem. Soc. 1954, 76: 111 -
13b
Anglea TA.Pinder AR. Tetrahedron 1987, 43: 5537 - 14
Kosugi H.Ku J.Kato M. J. Org. Chem. 1998, 63: 6939 - 15
Corey EJ.Burke HJ. J. Am. Chem. Soc. 1956, 78: 174 - 16
Catir M.Kilic H.Nardello-Rataj V.Aubry J.-M.Kazaz C. J. Org. Chem. 2009, 74: 4560 - 17
McLaughlin EC.Choi H.Wang K.Chiou G.Doyle MP. J. Org. Chem. 2009, 74: 730 - 18
Adam W.Balci M.Kilic H. J. Org. Chem. 2000, 65: 5926
References and Notes
General Procedure
for Oxidation of Benzylic and Allylic Substrates with PIFA/TBHP
System
(Caution! Although we
have never experienced an explosion, the oxidation of substrates
with PIFA/TBHP system should be carried out behind shields.)
To a solution of substrate (2 mmol) and anhyd TBHP (40 mmol) in
CH2Cl2 (10 mL) at -30 ˚C
was added NaHCO3 (20 mmol). Then a freshly prepared solution
of PIFA (5.0 mmol) in CH2Cl2 (10 mL) was added
over 2 h. The temperature was slowly increased to r.t. over 4 h.
On completion of reaction, the excess TBHP was reduced by adding
DMS¹8 (40 mmol) and Ti(Oi-Pr)4 (0.15
mmol) at r.t. while the reaction proceeding was monitored by peroxide
testing (KI, AcOH). The suspension was filtered, and the solution
was washed with sat. NaHCO3 solution and H2O.
The organic layer was dried over MgSO4, and the solvent
was removed at reduced pressure (20 ˚C/50
mbar). The products were purified on a silica gel column (40 g)
by eluting with hexane-EtOAc (95:5). The first fractions
gave iodobenzene. Further elution afforded analytically pure ketone.
The ketones 7a-l are known,
and analytical data were found to be identical with those reported.
9
H
-Fluoren-9-one (7b)
Yellow solid,
mp 81-82 ˚C (CH2Cl2-hexane). ¹H
NMR (200 MHz, CDCl3): δ = 7.63 (dd, J = 7.3, 1.0
Hz, 2 H), 7.30-7.20 (m, 2 H), 7.48-7.45 (m, 4
H). ¹³C NMR (50 MHz, CDCl3): δ = 195.8,
146.4, 136.6, 136.1, 131.0, 126.2, 122.2.
3,7,7-Trimethylbicyclo[4.1.0]hept-3-ene-2,5-dione
(7l)
Pale yellow solid; mp 94-96 ˚C
(CH2Cl2-hexane). ¹H
NMR (400 MHz, CDCl3): δ = 6.50-6.48
(m, 1 H), 2.33-2.29 (m, 2 H), 1.96 (d, J = 1.8
Hz, 3 H), 1.31 (s, 3 H) 1.30 (s, 3 H). ¹³C NMR
(100 MHz, CDCl3): δ = 195.2, 194.6,
150.2, 137.8, 40.0, 39.1, 33.9, 29.3, 16.4, 15.6.