10.1002/adsc.201700587
Advanced Synthesis & Catalysis
In conclusion, we have developed a metal-free and
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direct synthesis of 5-[(N,N-disulfonylamino)methyl]-
oxazoles based on the cycloisomerization–amination
sequence of N-propargyl carboxamides with
bis(sulfonyl)imides in the presence of PhI(OAc)2.
Also, this synthetic method could be successfully
extended to the catalytic version by iodine(III)
catalyst, which is in situ generated from iodobenzene
precatalyst with Oxone as a terminal oxidant in the
presence of TBAHSO4 as a phase transfer reagent.
Since such an introduction method of heteroatomic
functional groups except for oxygen functional
groups by iodine(III) catalysis have been less studied,
our findings provide not only an attractive procedure
for the access to the oxazoles bearing the nitrogen
functional group, but also a new reactivity of the
iodine(III) catalyst.
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Experimental Section
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Representative procedure for the cycloisomerization–
amination of amide 1a with (PhSO2)2NH
PhI(OAc)2 (154.6 mg, 0.48 mmol) was treated with
(PhSO2)2NH (285.4 mg, 0.96 mmol) in DCM-HFIP (3:1,
1.0 mL) at room temperature for 20 min. And then, to the
reaction mixture was added a solution of 1a (63.7 mg, 0.40
mmol) in DCM-HFIP (3:1, 1.0 mL). After being stirred at
same temparature for 8 h, the reaction mixture was diluted
with Et2O and filtered through a short alumina column.
Concentration of the filtrate to dryness and the subsequent
purification of the residue by silica gel column
chromatography (hexane/AcOEt = 3/1) gave 2a (136.9 mg,
75%).
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Representative procedure for the catalytic reaction of
amide 1a with (PhSO2)2NH
To a suspension of Oxone (368.9 mg, 0.60 mmol) and
TBAHSO4 (135.8 mg, 0.40 mmol) in HFIP (2.0 mL) was
added PhI (8.9 L, 0.08 mmol), (PhSO2)2NH (178.4 mg,
0.60 mmol) and 1a (63.7 mg, 0.40 mmol) in turn at room
temperature. After being stirred at same temperature for 24
h, the reaction mixture was diluted with Et2O and filtered
through a short alumina column. Concentration of the
filtrate to dryness and the subsequent purification of the
residue by silica gel column chromatography
(hexane/AcOEt = 3/1) gave 2a (98.6 mg, 54%).
[7] Synthesis of oxazoles bearing nitrogen functional
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R. Sarkar, M. Razzak, J. K. De Brabander, Org. Biomol.
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Acknowledgements
This work was partially supported by JSPS Grants-in-
Aid for Scientific Research (C) (Grant No 15K07852),
by the Society of Iodine Science and by the Takeda
Science Foundation. V.V.Z. is also thankful to the
National Science Foundation (CHE-1262479).
[8] Recent reviews: a) K. Muñiz, C. Martiίnez, J. Org.
Chem. 2013, 78, 2168; b) Y. Zhu, R. G. Cornwall, H.
Du, B. Zhao, Y. Shi, Acc. Chem. Res., 2014, 47, 3665;
c) K. Muñiz, C. Martiίnez, A. Iglesias, Chem. Rec.
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Int. Ed. 2009, 48, 1190; Angew. Chem. 2009, 121,
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4
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