Catalytic, Diastereoselective 1,2-Difluorination of Alkenes

Banik, Steven M.; Medley, Jonathan William; Jacobsen, Eric N.

doi:10.1021/jacs.6b02391

Cited by 245 publications

(121 citation statements)

References 56 publications

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“…However, trisubstituted cinnamamide derivatives undergo selective anchimeric assistance by the amide group en route to 1,2-difluorination products (i.e. 2s ) (33). According to the mechanism outlined in Fig.…”

mentioning

confidence: 99%

Catalytic, asymmetric difluorination of alkenes to generate difluoromethylated stereocenters

Banik

Medley

Jacobsen

2016

Science

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287

134

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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.

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confidence: 99%

Catalytic, asymmetric difluorination of alkenes to generate difluoromethylated stereocenters

Banik

Medley

Jacobsen

2016

Science

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287

134

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“…This problem was solved in 2016, with simultaneous reports from Jacobsen and Gilmour, who developed reaction conditions to generate aryl(difluoro)- 3 -iodanes in situ for alkene difluorination. 46,47 Both of their systems involved combinations of an aryl iodide, an external oxidant, and an HF source. The generation of hypervalent iodine in situ allows the aryl iodide to play a catalytic role in the mechanism, and substoichiometric quantities are employed.…”

Section: Synpacts Syn Lettmentioning

confidence: 99%

“…37 Jacobsen optimised a difluorination system that utilised the aryl iodide catalyst 24, which was found to be more efficient than 13 and is more amenable to the incorporation of chirality ( Figure 10A). 47 The optimised conditions included the use of mCPBA and Py•9HF, and were amenable to terminal alkenes and styrenyl substrates containing heterocy-…”

Section: Synpacts Syn Lettmentioning

confidence: 99%

Alkene Vicinal Difluorination: From Fluorine Gas to More Favoured Conditions

Doobary¹,

Lennox²

2020

Synlett

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Vicinal difluorinated alkanes are entities relevant to medicinal chemistry that are accessed through the difluorination of alkenes. This reaction has advanced from the use of highly reactive and unsafe reagents, which provide poor functional-group tolerance and selectivity, to the use of safer and more selective reagents that facilitate access to a broader scope of substrates. In this review article, we describe the details of these developments.1 Introduction2 Strategy 1: Ambiphilic Fluorine Sources3 Strategy 2: Oxidant and Fluoride4 Conclusions and Outlook

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“…Moreover, the difluorination of trisubstituted cinnamate derivatives provided a wide range of the desired products with 19:1 dr and 93% ee , respectively. The use of arenes and amides with alternative substitution gave different stereochemical outcome . Another example of an unprecedented alkene oxidation was developed by Jacobsen, who reported a unique catalytic approach to geminal difluorination products 91 (Scheme ) .…”

Section: Enantioselective Catalysismentioning

confidence: 99%

Enantioselective Iodine(I/III) Catalysis in Organic Synthesis

et al. 2018

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Chiral aryliodine(III)r eagents have provided an advancedc oncept for enantioselective synthesis and catalysis.W ith the advent of chiral iodine(I/III) catalysis,m anyd ifferent structures have been explored in the area. Thec urrently most prominent catalyst design is based on ar esorcinol core and the attachment of two lactic side chainsb earing ester or amide groups.T his enables ap rivileged modular catalyst synthesis,i nw hich fine-tuning with respect to the specificr eaction requirement is straightforward. Thep resent overview summarizes the structural variation and optimization of such chiral aryliodine catalysts andd iscusses structural properties of the active iodine(III) catalyst states.T he status quo of enantioselective iodine(I/III) oxidation catalysis with respect to intramolecular and intermolecular reaction control is reviewed, and specific aspects of the individual catalytic cycles are discussed. 1I ntroduction 2C hiral Aryliodine Catalysts 3E nantioselective Catalysis 3.1 Catalytic DearomatizationReactions 3.2 Formal C(sp 3 )Functionalization 3.3 Difunctionalization of Alkenes 4C onclusionScheme 14. Aryliodine-catalyzede nantioselective intermolecular para-dearomatization of phenols and aniline.Scheme15. Aryliodine-catalyzed enantioselective intermolecular para-dearomatization by Maruoka.Scheme30. Catalytic enantioselective version of the aminofluorination reaction.Scheme 28. Enantioselectiveo xidative cyclization of w-alkenylcarboxylic acids.Scheme29. Catalytic intramolecular diaminationo fa lkenes.

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Catalytic, Diastereoselective 1,2-Difluorination of Alkenes

Cited by 245 publications

References 56 publications

Catalytic, asymmetric difluorination of alkenes to generate difluoromethylated stereocenters

Catalytic, asymmetric difluorination of alkenes to generate difluoromethylated stereocenters

Alkene Vicinal Difluorination: From Fluorine Gas to More Favoured Conditions

Enantioselective Iodine(I/III) Catalysis in Organic Synthesis

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