Highly efficient synthesis of β-nitrate ester carboxamides through the ring-opening of 2-oxazolines

Qiao, Kai; Yuan, Xin; Wan, Li; Zheng, Ming‐Wei; Zhang, Dong; Fan, Bing-Bing; Di, Zhe-Chen; Fang, Zheng; Guo, Kai

doi:10.1039/c7gc02682j

Cited by 18 publications

(10 citation statements)

References 35 publications

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“…Focusing on the biological importance and industrial application of the 2‐oxazolines Guo et al. reported an efficient metal‐free protocol for the synthesis of β‐nitrate ester carboxamides ( 92 ) from 2‐substituted oxazolines ( 91 ) via ring‐opening of the oxazole ring (Scheme ) …”

Section: Outlines Of the Reactions Involving Tbnmentioning

confidence: 99%

“…Focusing on the biological importance and industrial application of the 2oxazolines Guo et al reported an efficient metal-free protocol for the synthesis of b-nitrate ester carboxamides (92)f rom 2substituted oxazolines (91)v ia ring-opening of the oxazole ring (Scheme66). [98] Based on the literature precedents at entative mechanism is proposed. Initially,T BN undergoes homolytic cleavaget og ive Scheme63.…”

Section: Nitrationmentioning

confidence: 99%

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tert‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis

Dahiya

Sahoo

Alam

et al. 2019

Chemistry An Asian Journal

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The upsurge interesti nt he development of efficient methodologies for the constructiono fn itrogen-containing frameworks via the use of expedient reagents have been creating ar enaissance in contemporary organic chemistry.I nt his perspective, tertbutyl nitrite (TBN) is an emerging building block. Due to its uniques tructuralf eatures, it shows differential reactivity under different reaction conditions. These diverse reactivities have resulted in the construction of ad iverse array of complex N-containing molecules. The primary objective of the presentr eview is to bring the latest findings of TBN in terms of its applications in reactions (oxidation, diazotization, nitrosation, nitration, oximation, N-synthon, and miscellaneous reactions) into the limelight.F or simplicity and brevity,r eactions in each section are explained with the mechanism of formation and selected examples are given.Scheme1.Differential reactivity of TBN. 4455 MinireviewScheme4.Visible-light-promoted synthesis of selenide ethers.Scheme5.Proposed mechanism for visible-light-promoted synthesis of selenide ethers.Scheme6.TBN-mediated synthesis of selenide ethers.Scheme7.Metal-free synthesis of 4-carbonylquinolines.Scheme8.Proposed mechanism for synthesis of 4-carbonylquinolines.Scheme9.TBN-mediated demethylative borylation of methylarenes.Scheme10. Plausible mechanism for demethylative borylation of methylarenes.Scheme11. Trifluoromethylation of various aromatic amine substrates.Scheme12. Copper-catalyzed isoperfluoropropylation of anilines.Scheme13. Plausible mechanism for Cu-catalyzed isoperfluoropropylation of anilines.Scheme14. TBN-mediateddiazotizative allylation of aromatic amines.Scheme15. Oxidativecyanomethylationo fa lkenes via CÀHb ond activation.Scheme16. TBN-mediatedand Cu-catalyzedsynthesis of thioether.

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Section: Outlines Of the Reactions Involving Tbnmentioning

confidence: 99%

Section: Nitrationmentioning

confidence: 99%

tert‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis

Dahiya

Sahoo

Alam

et al. 2019

Chemistry An Asian Journal

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“…Chemie cyclopropane 8 in 83 %yield, whereas its reduction with LAH followed by N-benzoylation afforded the methylamino derivative 9 in 63 %y ield over two steps.O fn ote,m ethylaminocyclopropanes constitute the core structure of marketed drugs such as Tasimelteon [16] and Levomilnacipran. [17] Finally, az inc-catalyzed [2+ +3] cycloaddition reaction of 3a with NaN 3 [18] gave the tetrazole-substituted cyclopropane 10, whereas ar eaction with aminoethanol and zinc chloride [19] afforded the oxazoline-functionalized cyclopropane 11 in good yields (39-84 %). In most cases,t he transformation of the nitrile group occurred with no erosion of enantiopurity (> 99 % ee,Scheme 3).…”

Section: Methodsmentioning

confidence: 99%

Highly Diastereo‐ and Enantioselective Synthesis of Nitrile‐Substituted Cyclopropanes by Myoglobin‐Mediated Carbene Transfer Catalysis

Chandgude

Fasan

2018

Angewandte Chemie

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Ac hemobiocatalytic strategy for the highly stereoselective synthesis of nitrile-substituted cyclopropanes is reported. The present approach relies on an asymmetric olefin cyclopropanation reaction catalyzedb ya ne ngineered myoglobin in the presence of ex situ generated diazoacetonitrile within acompartmentalized reaction system. This method enabled the efficient transformation of abroad range of olefin substrates at ap reparative scale with up to 99.9 %d ea nd ee and up to 5600 turnovers.T he enzymatic product could be further elaborated to affordavariety of functionalized chiral cyclopropanes.T his work expands the range of synthetically valuable,a biotic transformations accessible through biocatalysis and paves the waytothe practical and safe exploitation of diazoacetonitrile in biocatalytic carbene transfer reactions.The catalytic asymmetric cyclopropanation of alkenes with diazo compounds constitutes aconvenient and direct strategy for the construction of optically active cyclopropanes, [1] which are key structural motifs in numerous natural products and pharmaceuticals. [2] Within this structural class,c yano-substituted cyclopropanes represent particularly attractive building blocks owing to the versatility of the cyano group toward its interconversion to avariety of functional groups. [3] Moreover, cyano-functionalized cyclopropanes have been incorporated into pharmacologically active molecules,including the potent cathepsin Ki nhibitor Odanacatib. [4] Notable contributions from the Davies,C harette,a nd Zhang groups have recently introduced chemocatalytic protocols for the asymmetric synthesis of cyano-substituted cyclopropanes starting from donor-acceptor or acceptor-acceptor diazo compounds. [5] In stark contrast, methods for the asymmetric synthesis of cyano-substituted cyclopropanes using the acceptor-only diazo reagent diazoacetonitrile (N 2 CHCN) have remained elusive.A sa ni solated effort in this direction, chiral Ruporphyrins were reported to catalyze the cyclopropanation of styrene derivatives in the presence of pre-formed diazoacetonitrile (1a), but only with moderate diastereoselectivity (20-50 % de)a nd enantioselectivity (41-71 % ee) (Scheme 1). [6] More recently,the Koenigs group has reported the iron-catalyzed cyclopropanation of vinylarenes in the presence of in situ generated [7] diazoacetonitrile. [8] While offering good yields and scalability,t his method provides only moderate diastereoselectivity (2:1 to 7:1d .r.)a nd no enantioselectivity in the cyclopropanation reaction (Scheme 1). [8] Motivated by the shortcomings of current methodologies for this transformation, we have pursued and report herein the development of ab iocatalytic strategy for the highly stereoselective synthesis of nitrile-substituted cyclopropanes by myoglobin-catalyzed olefin functionalization with diazoacetonitrile.T his method provides ar ather general, efficient, and scalable route to enantiopure cyclopropanes incorporating ac yano group,w hich can be readily elaborated to afford variously functionalized ...

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“…Very recently, Zhang et al. developed a novel method for β‐nitrate ester carboxamides synthesis using the non‐corrosive tert‐butyl nitrite (TBN) as the nitro source and easily available oxygen as the oxidant, providing a facile method to synthesis of nicorandil . In addition, there are many outstanding reports about halogenation reactions .…”

Section: Introductionmentioning

confidence: 99%

Metal–free Efficient Method for the Synthesis of N‐(2‐haloethyl)benzamides through the Ring‐opening of2‐oxazolines

Guan¹,

Luan²,

Patiguli³

et al. 2019

ChemistrySelect

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An efficient, metal-free C-H halogenated method for the synthesis of β-halogenated carboxamides using non-corrosive NXS (X=Cl, Br) as the halogenated source and ammonium sulfocyanide (NH 4 SCN) as the additive was proposed and accomplished. Various substituted 2-oxazolines efficiently afforded the corresponding β-halogenated carboxamides via a ring-opening reaction in good yields. The characteristic features of this reaction include readily available materials, mild reaction conditions and functional groups tolerance.[a] Dr.

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Highly efficient synthesis of β-nitrate ester carboxamides through the ring-opening of 2-oxazolines

Abstract: A novel method for the synthesis of β-nitrate ester carboxamides using non-corrosive tert-butyl nitrite (TBN) as the nitro source and easily available oxygen as the oxidant has been developed.

Cited by 18 publications

References 35 publications

tert‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis

tert‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis

Highly Diastereo‐ and Enantioselective Synthesis of Nitrile‐Substituted Cyclopropanes by Myoglobin‐Mediated Carbene Transfer Catalysis

Metal–free Efficient Method for the Synthesis of N‐(2‐haloethyl)benzamides through the Ring‐opening of2‐oxazolines

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