- TRIFLUOROMETHYL THIOLATION AGENT, TRIFLUOROMETHYL THIOLATION METHOD, AND N-(SUBSTITUTED SULFONYL)-N-[(TRIFLUOROMETHYL)THIO]SUBSTITUTED SULFONAMIDE COMPOUND
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PROBLEM TO BE SOLVED: To provide a new trifluoromethyl thiolation agent, a trifluoromethyl thiolation method, and an N-(substituted sulfonyl)-N-[(trifluoromethyl)thio]-substituted sulfonamide compound. SOLUTION: Provided is a trifluoromethyl thiolation agent represented by a compound represented by formula (I) or the like:(R1 and R2 respectively independently denote a halogeno group, cyano group, unsubstituted/substituted alkyl group, unsubstituted/substituted cycloalkyl group, unsubstituted/substituted alkenyl group, unsubstituted/substituted alkynyl group, unsubstituted/substituted aryl group, unsubstituted/substituted heterocyclic group, unsubstituted/substituted alkoxy group, unsubstituted/substituted aryloxy group, an unsubstituted/substituted heterocyclic oxy group or the like; R1 and R2 may coupled to form a ring). SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0063; 0069
(2017/08/02)
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- Copper- and phosphane-free sonogashira coupling of arenediazonium o-benzenedisulfonimides
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Arenediazonium o-benzenedisulfonimides can be used as efficient reagents in Sonogashira coupling reactions. In this work, reactions were carried out in DMSO under very mild conditions (without copper or phosphanes), and gave rise to arylated alkynes in good to excellent yields (25 examples, average yield 83 %). o-Benzenedisulfonimide could be recovered from all the reactions in yields of >80 %, so it could be recycled for the preparation of other diazonium salts. Mechanistic insights revealed the fundamental roles of DMSO and the anion of o-benzenedisulfonimide in the formation of the catalyst, and also the importance of DMSO in the catalytic cycle. The Sonogashira coupling between are diazonium o-benzenedisulfonimides and terminal alkynes is a powerful method for the formation of arylated alkynes. No copper, phosphanes, bases, or co-catalysts are needed. Mechanistic insights highlighted the fundamental roles of DMSO and o-benzenedisulfonimide in the formation of the catalyst, and also the important role of DMSO in the catalytic cycle. Copyright
- Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano
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p. 598 - 605
(2014/02/14)
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- Reactions of arenediazonium o-benzenedisulfonimides with aliphatic triorganoindium compounds
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The reaction of various arenediazonium o-benzenedisulfonimides with aliphatic triorganoindium compounds is described. Surprisingly, with triethyl- or tributylindium we obtained N-ethyl- or N-butylanilines, respectively. This is the first case in which, at least formally, the reactive site of a diazonium salt is the nitrogen atom directly bonded to the aromatic ring. In contrast, with trimethylindium we obtained only formaldehyde (aryl)hydrazones. In order to explain the difference between trimethyl- and triethylindium we have proposed some reaction mechanisms, supported by detailed density functional (DFT) calculations. The possible role of diazene/hydrazone tautomerism initially assumed was discarded and therefore three mechanisms for the key step (nucleophilic addition of the trialkylindium to the N=N double bond of diazene) were studied. For the favoured mechanism there is a difference in the energy barriers of 2 kcalmol-1 between the reactions with trimethyl- and triethylindium. This difference is explained on the basis of the different C-In bond energies in the two organometallics and it is assumed to be enough to explain their different behaviour under the experimental conditions. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano,Ghigo, Giovanni
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scheme or table
p. 862 - 868
(2009/04/11)
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- Palladium-catalyzed cross-coupling alkylation of arenediazonium o-benzenedisulfonimides
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Arenediazonium o-benzenedisulfonimides were reacted with tetramethyltin, tetrabutyltin or trialkylboranes. The reactions, carried out in the presence of palladium(II) derivatives as precatalysts, gave the methylation and alkylation products with good over
- Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano
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p. 474 - 478
(2008/09/21)
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- Benzylation of alcohols and phenols with N-(4-methoxybenzyl)-o- benzenedisulfonimide
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N-(4-methoxybenzyl)-o-benzene disulfonimide was prepared from o- benzenedisulfonyl chloride and 4-methoxybenzylamine in dichloromethane. Reaction of this compound with alcohols or phenols undere basic conditions gave the corresponding 4-methoxybenzyl ethers in good yields. Primary alkylamines were converted to the corresponding alcohols by treating the benzenedisulfonimido derivative with aqueous KOH in DMF solution.
- Carlsen, Per H.J.
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p. 1799 - 1802
(2007/10/03)
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