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Organic Process Research & Development
(
c) McKittrick, B. A.; Ganem, B. Advances in the chemistry of 2,3-
The combined organic phases are then dried over
anhydrous MgSO , filtered and evaporated under
reduced pressure to afford a crude residue, which is
purified by flash column chromatography over silica gel.
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3
4
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epoxyalcohols. New methodology for contra-trans-diaxial opening
and selective enediol oxidation. J. Org. Chem. 1985, 50, 5897–5898.
4
(
7) For selected examples of protecting group removal, see: (a)
Chandrasekhar, S.; Sumithra, G.; Yadav, J. S. Deprotection of mono
and dimethoxy phenyl methyl ethers using catalytic amounts of DDQ.
Tetrahedron Lett. 1996, 37, 1645−1646. (b) Rahim, M. A.; Matsumu-
ra, S.; Toshima, K. Photo-induced aromatic assembly of benzocyclo-
alka[1,2-b] furan and spiro[furan-2(3H),1′-benzocycloalkane] deriva-
tives. Tetrahedron Lett. 2005, 46, 7307–7309. (c) Horita, K.; Yoshi-
oka, T.; Tanaka, T.; Oikawa, Y.; Yonemitsu, O. On the selectivity of
deprotection of benzyl, mpm (4-methoxybenzyl) and dmpm
(3,4-dimethoxybenzyl) protecting groups for hydroxy functions.
Tetrahedron, 1986, 42, 3021−3028.
ASSOCIATED CONTENT
S
Supporting Information
The Supporting information is available free of charge on the
ACS Publications website. Details of experimental procedures,
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H and C NMR spectra, DSC study.
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AUTHOR INFORMATION
Corresponding Author
(
8) For selected examples of aromatization, see: (a) Ohmura, T.;
Masuda, K.; Takase, I.; Suginome, M. Palladium-catalyzed silylene-
,3-diene [4 + 1] cycloaddition with use of (aminosilyl)boronic esters
as synthetic equivalents of silylene. J. Am. Chem. Soc. 2009, 131,
6624–16625. (b) Manning, J. R.; Davies, H. M. L. One-pot synthesis
1
*
*
E-mail: s.arseniyadis@qmul.ac.uk
E-mail: alexandre.jean@servier.com
1
of highly functionalized pyridines via a rhodium carbenoid induced
ring expansion of isoxazoles. J. Am. Chem. Soc. 2008, 130, 8602–
ORCID
Stellios Arseniyadis: 0000-0001-6831-2631
8
603. (c) Ploypradith, P.; Petchmanee, T.; Sahakitpichan, P.; Litvinas,
N. D.; Ruchirawat, S. Total synthesis of natural and unnatural lamel-
larins with saturated and unsaturated D-rings. J. Org. Chem. 2006, 71,
Author Contributions
The manuscript was written through contributions of all authors.
All authors have given approval to the final version of the manu-
script.
9
440–9448. (d) Shimizu, M.; Takahashi, A.; Kawai, S. Efficient
pyrrole synthesis using double nucleophilic addition to
α,β-unsaturated imines with plural nucleophiles. Org. Lett. 2006, 8,
3
585–3587. (e) Pla, D.; Marchal, A.; Olsen, C. A.; Albericio, F.;
Alvarez, M. Modular total synthesis of lamellarin D. J. Org. Chem.
005, 70, 8231–8234. (f) Wurz, R. P.; Charette, A. B. Doubly activat-
ed cyclopropanes as synthetic precursors for the preparation of
-nitro- and 4-cyano-dihydropyrroles and pyrroles. Org. Lett. 2005, 7,
Notes
The authors declare no competing financial interest.
2
ACKNOWLEDGMENT
4
This research was supported by Queen Mary University of
London and Oril Industrie.
2313–2316.
(9) For selected examples of benzylic acetoxylation, see:
(a) Kumar, V.; Sharma, A.; Sharma, M.; Sharma, U. K.; Sinha, A. K.
DDQ catalyzed benzylic acetoxylation of arylalkanes: a case of
exquisitely controlled oxidation under sonochemical activation.
Tetrahedron 2007, 63, 9718–9723. (b) Marcantoni, E.; Petrini, M.;
Profeta, R. Synthesis of advanced intermediates for the preparation of
aza-analogues of podophyllotoxin. Tetrahedron Lett. 2004, 45, 2133–
2136.
(10) Li, C. J. Cross-dehydrogenative coupling (CDC): Exploring
C−C bond formations beyond functional group transformations. Acc.
Chem. Res. 2009, 42, 335–344.
(11) For selected examples of oxidative cyclizations, see: (a) Liu,
L.; Floreancig, P. E. Cyclization reactions through DDQ-mediated
vinyl oxazolidinone oxidation. Org. Lett. 2009, 11, 3152–3155.
(b) Tu, W. Y.; Floreancig, P. E. Oxidative carbocation formation in
macrocycles: Synthesis of the neopeltolide macrocycle. Angew.
Chem. Int. Ed. 2009, 48, 4567–4571.
REFERENCES
(
1) (a) Bäckvall, J. E. Modern Oxidation Methods, VCH Wiley,
Weinheim, 2004, pp 83-118. (b) Hundlucky, M. Oxidation in Organic
Chemistry, American Chemical Society, Washington, DC, 1990.
(c) Caron, S.; Dugger, R. W.; Ruggeri, S. G.; Ragan, J. A.; Ripin, D.
H. B. Large-scale oxidations in the pharmaceutical industry. Chem.
Rev. 2006, 106, 2943−2989.
(
2) (a) Tojo, G.; Fernández, M. Oxidation of alcohols to aldehydes
and ketones: A guide to current common practice; Springer Science
Business Media: New York, 2010. (b) Haines, A. Methods for oxida-
tion of organic compounds V2: Alcohols, alcohol derivatives, alkyl
halides, nitroalkanes, alkyl azides, carbonyl compounds hydroxy-
arenes and aminoarenes; Academic Press: London, 1988. (c) Fuchs, P.
L. Handbook of Reagents for Organic Synthesis: Catalytic Oxidation
Reagents; Wiley & Sons: Chichester, UK, 2013.
(3) Mallat, T.; Baiker, A. Oxidation of alcohols with molecular ox-
ygen on solid catalysts. Chem. Rev. 2004, 104, 3037−3058.
(12) Zhai, L.; Shukla, R.; Rathore, R. Oxidative C−C bond for-
mation (Scholl reaction) with DDQ as an efficient and easily recycla-
ble oxidant. Org. Lett. 2009, 11, 3474–3477.
(13) LD50 of 82 mg/kg.
(14) Liu, L.; Floreancig, P. E. 2,3-Dichloro-5,6-dicyano-1,4-
(
4) For reviews on hypervalent iodine reagents see: (a) Banks, D.
F. Organic Polyvalent Iodine Compounds. Chem. Rev. 1966, 66,
43−266. (b) Stang, P. J.; Zhdankin, V. V. Organic polyvalent iodine
2
compounds. Chem. Rev. 1996, 96, 1123−1178; (c) A. Varvoglis,
2
benzoquinone-catalyzed reactions employing MnO as a stoichio-
Hypervalent iodine in organic synthesis; Academic Press: San Diego,
metric oxidant. Org. Lett. 2010, 12, 4686−4689.
1
997; (d) Stang, P. J.; Zhdankin, V. V. Recent developments in the
chemistry of polyvalent iodine compounds. Chem. Rev. 2002, 102,
523−2584; (e) Hypervalent Iodine Chemistry; Wirth, T., Ed.;
(15) Cosner, C. C.; Cabreara, P. J.; Byrd, K. M.; Thomas,
A. M. A.; Helquist, P. Selective oxidation of benzylic and allylic
2
alcohols using Mn(OAc)
benzoquinone. Org. Lett. 2011, 13, 2071−2073.
(16) Hu, Y.; Chen, L.; Li, B. Fe(NO /2,3-dichloro-5,6-dicyano-
3
/catalytic 2,3-dichloro-5,6-dicyano-1,4-
Springer: Heidelberg, 2003.
(5) (a) Bharate, S. B. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone
3 3
)
(
2
1
DDQ). Synlett 2006, 496–497. (b) Walker, D.; Hiebert, J. D.
,3-Dichloro-5,6-dicyanobenzoquinone and its reactions. Chem. Rev.
967, 67, 153−195.
1,4-benzoquinone (DDQ): An efficient catalyst system for selective
oxidation of alcohols under aerobic conditions. Catal. Commun. 2018,
103, 42–46.
(
6) For selected examples of alcohol oxidation, see: (a) Peng, K.;
(17) Mozina, S.; Iskra, J. Aerobic oxidation of secondary alcohols
with nitric acid and iron(III) chloride as catalysts in fluorinated alco-
hol. J. Org. Chem. 2019, 84, 14579−14586.
(18) Shen, Z.; Dai, J.; Xiong, J.; He, X.; Mo, W.; Hu, B.; Sun, N.;
Hu, X. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)/tert-butyl
Chen, F. X.; She, X. G.; Yang, C. H.; Cui, Y. X.; Pan, X. F. Selective
oxidation of benzylic or allylic hydroxyl group of sec-1,2-diols.
Tetrahedron Lett. 2005, 46, 1217–1220. (b) Mori, K.; Koseki, K.
Synthesis of trichostatin a, a potent differentiation inducer of friend
leukemic cells, and its antipode. Tetrahedron 1988, 44, 6013–6020.
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