Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes

Gilbert, Bradley B.; Eey, Stanley T.-C.; Ryabchuk, Pavel; Garry, Olivia L.; Denmark, Scott E.

doi:10.1016/j.tet.2019.05.054

Cited by 40 publications

(25 citation statements)

References 60 publications

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“…Catalysts were selected for evaluation on the basis of their performance (rate of reaction and selectivity) in the enantioselective syn-dichlorination of alkenes. 43 Cinnamyl benzyl ether 4 was selected for optimization of enantiomeric ratio because it afforded better enantioselectivity compared to terminal olefin 2. Catalyst 6 afforded very good yield and modest enantioselectivity.…”

Section: Resultsmentioning

confidence: 99%

“…The stereochemical course of the reaction was established by single-crystal X-ray diffraction of product 5.The absolution configuration (1R,2S)-5, is consistent with the absolute configuration found for a syndichlorination product formed by structurally related catalysts. 43…”

Section: Resultsmentioning

confidence: 99%

“…A recent report from these laboratories disclosed the design and synthesis of chiral, enantioenriched diselenides for the development of a catalytic, enantioselective syndichlorination of alkenes, by employing a Se(II)/Se(IV) redox cycle. 43,44 Unfortunately, enantioselectivities are modest using a wide variety of structurally distinct diselenides. The modest selectivities likely result from the reversibility of seleniranium ion formation (the enantiodetermining step) and slow intermolecular displacement of the arylselenium(IV)…”

Section: Introductionmentioning

confidence: 99%

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Catalytic, Enantioselective Syn-Diamination of Alkenes

Tao¹,

Gilbert²,

Denmark

2019

Preprint

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The enantioselective, vicinal diamination of alkenes represents one of the stereocontrolled additions that remains an outstanding challenge in organic synthesis. A general solution to this problem would enable the efficient and selective preparation of widely useful, enantioenriched diamines for applications in medicinal chemistry and catalysis. In this Article we describe the first enantioselective, syn-diamination of simple alkenes mediated by a chiral, enantioenriched organoselenium catalyst together with a N,N’-bistosyl urea as the bifunctional nucleophile and N-fluorocollidinium tetrafluoroborate as the stoichiometric oxidant. Diaryl, aryl-alkyl, and alkyl-alkyl olefins bearing a variety of substituents are all diaminated in consistently high enantioselectivities selectivities but variable yields. The reaction likely proceeds through a Se(II)/Se(IV) redox catalytic cycle reminiscent of the syn-dichlorination reported previously. Furthermore, the syn-stereospecificity of the transformation shows promise for highly enantioselective diaminations of alkenes with no strong steric or electronic bias.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Catalytic, Enantioselective Syn-Diamination of Alkenes

Tao¹,

Gilbert²,

Denmark

2019

Preprint

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“…[125] Such a challenge was thereby addressed by Scott et. al., [136] after successful development of strategy that ensures suprafacial dichlorination of alkenes 68 to produce syn-dichorinated products 69 in the presence of chiral diaryl diselenide catalysts. Amongst twentythree catalysts that were assessed, 70 yielded the dichloro product with highest enantioselectivity of 76 : 24 (Scheme 30).…”

Section: Organoselenium Reagents As Regioselective and Stereoselectivmentioning

confidence: 99%

Insights into the Recent Synthetic Advances of Organoselenium Compounds

2021

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The ever-growing interest for organoselenium compounds amongst the chemists has made commendable impact in the field of medicinal chemistry, material chemistry, chemical biology and biochemistry. Researchers have progressively contributed in the development of organoselenium compounds over the years which has been periodically reviewed. On the similar note, this review attempts at providing an overview of the recent advances made in organoselenium chemistry while covering their catalytic indulgence in different transformational approaches, their role in asymmetric synthesis, and synthetic approaches steering their synthesis. These approaches encompass selenofunctionalization and/or cyclization, electrochemical selenylation, bromolactonization, [2,3]-or [1,2]-sigmatropic rearrangement reactions among others. Herein, we have focused on the synthetic approaches developed for the past three years that have not been covered in previously reviewed scientific material. With the knowledge of the recent progress covered, this review could contribute towards future development of organoselenium compounds along with the improvement of the current status.

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“…In 2019, the group of Denmark rendered the transformation asymmetric by switching to chiral diselenides, such as 113 , as catalyst precursors (Scheme 23). [59] …”

Section: Dichlorination Dibromination and Mixed Dihalogenationsmentioning

confidence: 99%

Enantioselective Dihalogenation of Alkenes

Bock

Guria

Wedek

et al. 2021

Chemistry A European J

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The dihalogenation of alkenes is one of the classic reactions in organic chemistry and a prime example of an electrophilic addition reaction. The often observed anti‐selectivity in this addition reaction can be explained by the formation of a haliranium‐ion intermediate. Although dihalogenations have been studied for more than a century, the development of reagent‐controlled, enantioselective dihalogenation has proved to be very difficult. Only recently, significant progress has been achieved. In this review, an overview on current method development in enantioselective dihalogenation is provided and mechanistic aspects that render this transformation challenging are discussed.

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Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes

Cited by 40 publications

References 60 publications

Catalytic, Enantioselective Syn-Diamination of Alkenes

Catalytic, Enantioselective Syn-Diamination of Alkenes

Insights into the Recent Synthetic Advances of Organoselenium Compounds

Enantioselective Dihalogenation of Alkenes

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