Trifluoroacetonyl radicals: a versatile approach to trifluoromethyl ketones

Denieul, Marie-Pierre; Quiclet‐Sire, Béatrice; Zard, Samir Z.

doi:10.1039/cc9960002511

Cited by 41 publications

(20 citation statements)

References 16 publications

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“…The synthesis of trifluoromethyl-substituted tricyclic indoline 47 illustrates both the ease of accessing trifluoromethylk e-tones such as precursor 23 aa by addition of the at rifluoroacetonyl xanthate to alkenes [29] and the ability,m ore generally,o f preparing fluorinated compounds. [30] Higher polycyclici ndolines can be obtained by startingw ith adducts derived from cyclic ketonyl xanthates.…”

Section: Radical Cyclizations Onto Aromatic Ringsmentioning

confidence: 99%

The Xanthate Route to Indolines, Indoles, and their Aza Congeners

Zard

2020

Chemistry A European J

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Convergentr outes to av ariety of indolines, indoles, oxindoles, and their aza analogues involving radical additions of xanthates are described. Three approaches are summarized. The first is the least general and relies on the generation of aryl or heteroaryl radicals startingf rom diazonium salts. The second involves radical addition to N-allylanilines followed by ring-closure onto the aromatic core. A large varietyo fi ndolines and azaindolines can thus be obtained and, in many cases, converted into the corresponding indoles and azaindoles by variousm ethods. Thes ynthesiso f novel fluoroazaindolines and fluoroazaindoles by ar are homolytic ipso-substitution of fluorine atoms is particularly noteworthy.T he last approachh inges on the direct modification of indoles by radical addition to the pyrrole subunit of the indolen ucleus. Application of this methodology to the total synthesis of melatonin andt he alkaloids mersicarpine, caulerpine, and the pentacyclic skeleton of tronocarpine is briefly discussed. Mosto ft he compounds described herein would be difficult to obtain by more traditional routes.

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Section: Radical Cyclizations Onto Aromatic Ringsmentioning

confidence: 99%

The Xanthate Route to Indolines, Indoles, and their Aza Congeners

Zard

2020

Chemistry A European J

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“…Since its discovery, more than 2000 additions have been accomplished using over a hundred different xanthates. The examples collected in Scheme illustrate additions to just one alkene, allyl trimethylsilane …”

Section: Examples Of Practical Applications Of the Addition Of Xanthamentioning

confidence: 99%

Some intriguing mechanistic aspects of the radical chemistry of xanthates

Zard

2012

J of Physical Organic Chem

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International audienceXanthates are exceedingly useful substrates for intermolecular and intramolecular radical additions, even to unactivated alkenes. Various functional groups can be brought together under mild, neutral conditions, thus providing tremendous opportunities for organic synthesis. Because the products of the additiontransfer process are also xanthates, iteration allows the formation of block polymers by a controlled radical polymerisation (the RAFT/MADIX technology). The present overview concentrates on mechanistic and unexpected aspects of this chemistry, which may be of particular interest to physical organic chemists. Copyright (C) 2012 John Wiley & Sons, Ltd

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“…Thus, xanthate 66, the preparation of which is described in Scheme 5.18, adds smoothly to allyl trimethylsilane to give the corresponding adduct 90 [25d]. In the same manner, xanthates 91, 92 (neoPn = neopentyl) and 93 furnish fluorinated adducts 94, 95 and 96 respectively in generally high yield [27][28][29]. The efficient synthesis of bisphosphonate 98 from precursor 97 is also worthy of mention [20b].…”

Section: Some Synthetic Applications Of the Degenerative Radical Tranmentioning

confidence: 99%

“…Using the same simple experimental procedure, it is possible to perform the radical addition on much more complex olefins, as demonstrated by the three transformations in Scheme 5.25 involving trifluoromethyl ketone xanthate (92), a very convenient source of trifluoroacetonyl radicals [28]. Trifluoromethyl ketones attached to structures as complex as pleuromutilin, a terpene antibiotic, can be readily assembled without the need for protection of the other functional groups present [30].…”

Section: Some Synthetic Applications Of the Degenerative Radical Tranmentioning

confidence: 99%