Substituent effects in the fluorination-rearrangement of 1,1-diarylethenes with aryliodine(III) difluorides

Patrick, Timothy B.; Scheibel, Jeffrey J.; Hall, W. E.; Lee, Young Ho

doi:10.1021/jo01310a043

Cited by 53 publications

(8 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Some five-, six-, or seven-membered ring-contracted products 94 , 96 were synthesized from the cyclohexene, cycloheptene, or cyclooctene derivatives 93 , 95 using (difluoroiodo)toluene 71 (Scheme ). (Difluoroiodo)toluene 71 reacts with aryl-substituted alkenes to afford the rearranged, geminal difluorides, formed by migration of the aryl group. ,,, …”

Section: Synthetic Applications Of Trivalent Iodine Compoundsmentioning

confidence: 99%

See 1 more Smart Citation

Advances in Synthetic Applications of Hypervalent Iodine Compounds

2016

View full text Add to dashboard Cite

The preparation, structure, and chemistry of hypervalent iodine compounds are reviewed with emphasis on their synthetic application. Compounds of iodine possess reactivity similar to that of transition metals, but have the advantage of environmental sustainability and efficient utilization of natural resources. These compounds are widely used in organic synthesis as selective oxidants and environmentally friendly reagents. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various oxidations, rearrangements, aminations, C−C bond-forming reactions, and transition metal-catalyzed reactions are summarized and discussed. Recent discovery of hypervalent catalytic systems and recyclable reagents, and the development of new enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important achievement in the field of hypervalent iodine chemistry. One of the goals of this Review is to attract the attention of the scientific community as to the benefits of using hypervalent iodine compounds as an environmentally sustainable alternative to heavy metals.

show abstract

Section: Synthetic Applications Of Trivalent Iodine Compoundsmentioning

confidence: 99%

“…(Difluoroiodo)toluene 71 reacts with arylsubstituted alkenes to afford the rearranged, geminal difluorides, formed by migration of the aryl group. 82,228,246,247 3.2.2. (Dichloroiodo)arenes.…”

Section: Hypervalent Iodine Halidesmentioning

confidence: 99%

Advances in Synthetic Applications of Hypervalent Iodine Compounds

2016

View full text Add to dashboard Cite

show abstract

“…Although the substrate scope of this transformation is rather limited, the method allowed in general for the conversion of tri-(-47b) and monosubstituted alkenes (-47d) as well as for starting materials with differently equipped aryl portions, such as 46c (Scheme 11b). 27c,28c, 49 Thorough mechanistic investigations on this type of fluorination reaction were conducted by the groups of i.a. Patrick 49 and Zupan 28c,50 with particular emphasis on shedding light on the rearrangement.…”

Section: Geminal Difluorination Of Alkenesmentioning

confidence: 99%

Hypervalent iodine(iii) fluorinations of alkenes and diazo compounds: new opportunities in fluorination chemistry

2016

View full text Add to dashboard Cite

The fluorination of organic molecules is a rapidly evolving and exciting field in synthesis, which still poses huge challenges despite the advances made in the past decades. Hypervalent iodine(iii) reagents, which have already proven their versatility as synthetic tools in organic chemistry, are currently on the rise in fluorination chemistry. With their ability to break new mechanistic grounds, they grant access to completely new reactivities and thus also to novel fluorinated structural scaffolds. This review aims to provide an overview of the achievements made in the iodine(iii) mediated fluorinations of aliphatic Csp-carbon atoms with special focus on the opportunities provided by this exciting class of hypervalent substances.

show abstract

“…In particular, hypervalent iodoarenes have been demonstrated to mediate the 1,1-difluorinative rearrangement of both cyclic (27) and acyclic (28, 29, 30, 31) alkyl-substituted styrenes through the intermediacy of phenonium ion intermediates (e.g., III , Fig. 1E), and Kitamura and coworkers have reported a catalytic protocol for the conversion of unfunctionalized, terminal styrenes to achiral difluorinated products (32).…”

mentioning

confidence: 99%

Catalytic, asymmetric difluorination of alkenes to generate difluoromethylated stereocenters

Banik

Medley

Jacobsen

2016

Science

287

146

View full text Add to dashboard Cite

Difluoromethyl groups possess specific steric and electronic properties that invite their use as chemically inert surrogates of alcohols, thiols, and other polar functional groups important in a wide assortment of molecular recognition processes. We report here a method for the catalytic, asymmetric, migratory geminal difluorination of β-substituted styrenes to access a variety of products bearing difluoromethylated tertiary or quaternary stereocenters. The reaction uses commercially available reagents (mCPBA and HF•pyridine) and a simple chiral aryl iodide catalyst, and is carried out readily on gram scale. Substituent effects and temperature-dependent variations in enantioselectivity suggest that cation-π interactions play an important role in stereodifferentiation by the catalyst.

show abstract

Substituent effects in the fluorination-rearrangement of 1,1-diarylethenes with aryliodine(III) difluorides

Cited by 53 publications

References 0 publications

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Hypervalent iodine(iii) fluorinations of alkenes and diazo compounds: new opportunities in fluorination chemistry

Catalytic, asymmetric difluorination of alkenes to generate difluoromethylated stereocenters

Contact Info

Product

Resources

About