<i>tert</i>-Butyl Nitrite: Organic Redox Cocatalyst for Aerobic Aldehyde-Selective Wacker–Tsuji Oxidation

Ning, Xiaojuan; Wang, Meimei; Yao, Chuan‐Zhi; Chen, Xianmin; Kang, Yan‐Biao

doi:10.1021/acs.orglett.6b01165

Cited by 68 publications

(30 citation statements)

References 37 publications

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“…The reactionp roceeds well with av ariety of alkenes in high re-gioselectivity and good to moderate yields. [14] The same group in 2018m odified the condition and developed ar egioselective switchable aerobic Wacker-Tsuji oxidationb ys olely switching the solventf rom dry to wet alcohol. The reactioni nd ry tBuOH is aldehyde selective and follows anti-Markovnikov's rule which is reverseinw et EtOH.…”

Section: Oxidationmentioning

confidence: 99%

“…developed an aldehyde‐selective aerobic Wacker‐Tsuji oxidation where TBN served as organic redox co‐catalyst, substituting other transition metals such as silver or copper. The reaction proceeds well with a variety of alkenes in high regioselectivity and good to moderate yields . The same group in 2018 modified the condition and developed a regioselective switchable aerobic Wacker‐Tsuji oxidation by solely switching the solvent from dry to wet alcohol.…”

Section: Outlines Of the Reactions Involving Tbnmentioning

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: Oxidationmentioning

confidence: 99%

Section: Outlines Of the Reactions Involving Tbnmentioning

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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“…NMR spectra and physical properties matched those reported in literature. 29 In a round bottom flask, aniline (2.19 mL, 24 mmol) was dissolved in 10 mL of MeCN. S5 (1.81 g, 8 mmol) was added and the reaction mixture was refluxed for three hours.…”

Section: S552 Intramolecular Precursorsmentioning

confidence: 99%

Reverse Polarity Reductive Functionalization of Tertiary Amides via a Dual Iridium-Catalyzed Hydrosilylation and Single Electron Transfer Strategy

et al. 2020

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A new strategy for the mild generation of synthetically valuable α-amino radicals from robust tertiary amide building blocks has been developed. By combining Vaska's complex-catalyzed tertiary amide reductive activation and photochemical single electron reduction into a streamlined tandem process, metastable hemiaminal intermediates were successfully transformed into nucleophilic α-amino free radical species. This umpolung approach to such reactive intermediates was exemplified through coupling with an electrophilic dehydroalanine acceptor, resulting in the synthesis of an array of α-functionalized tertiary amine derivatives, previously inaccessible from the amide starting materials. The utility of the strategy was expanded to include secondary amide substrates, intramolecular variants and late stage functionalization of an active pharmaceutical ingredient. DFT analyses were used to establish the reaction mechanism and elements of the chemical system that were responsible for the reaction's efficiency. Scheme 1. α-Functionalization strategies for amine synthesis from tertiary amides Scheme 3. Optimization studies for (A) Vaska's catalyzed amide hydrosilylation. (B) The photocatalytic reductive coupling of the silyl hemiaminal intermediate with DHA derivative. stituted structures delivered tertiary amine products, although a steric increase vs. reaction efficiency trend was observed. 19 Intramolecular Cyclization. We recognized the opportunity that this tandem amide activation protocolthrough tethering an alkene acceptor to the alkyl chain of the amide starting material-could be suitably leveraged towards the synthesis of complex heterocyclic amine frameworks. Accordingly, model substrates bearing a pendant α,β-unsaturated ester (1s-1t) were prepared, but initial studies demonstrated that these motifs did not readily undergo hydrosilylation using Vaska's catalyst (only around 80% conversion was achieved after 8 hours of reaction time), and furthermore significant quantities of over reduction side-product were isolated following the photocatalytic step. 20 Nevertheless, these initial challenges were circumvented when a derivative of Vaska's complex bearing triphenylphosphite ligands-previously reported by Nagashima 21-was employed in the hydrosilylation step instead (Scheme 5). Pleasingly, clean conversion to a stable silyl hemiaminal species was achieved within one hour, and subsequent subjection to the optimized photoredox conditions delivered the desired cyclic pyrrolidine (4s) and piperidine (4t) products in good yields. Scheme 5. Extension of the Vaska-photoredox system for reductive cyclization of tertiary amides Secondary Amide Activation. Recent endeavors by Chida and Sato, and Huang have demonstrated the utility of [Ir(COE)2Cl]2 complex in conjunction with Et2SiH2 reductant for the nucleophilic reductive functionalization of secondary amide building blocks, affording the corresponding α-branched secondary amine products. 4e,f Scheme 6. Reverse polarity, photocatalytic reductive functionalization of seconda...

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“…There are several types of substrates that afford AM products, including alkenes with directing groups such as oxygen or nitrogen functionalities (allylic ethers, allylic esters, homoallylic alcohols, homoallylic ethers, homoallylic esters, allylic amines, allylic amides, allylic phthalimides etc.) and dienes [16–18,21,23–28] . Several reaction conditions influence the regioselectivity of aromatic terminal alkenes [6,16–18,21,29] .…”

Section: Introductionmentioning

confidence: 99%

“…and dienes. [16][17][18]21,[23][24][25][26][27][28] Several reaction conditions influence the regioselectivity of aromatic terminal alkenes. [6,[16][17][18]21,29] This will be discussed in more detail at the beginning of Sections 2.1 and 3.1.…”

Section: Introductionmentioning

confidence: 99%

Realization of Anti‐Markovnikov Selectivity in Pd‐Catalyzed Oxidative Acetalization and Wacker‐Type Oxidation of Terminal Alkenes

Ura

2021

The Chemical Record

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Catalytic oxidative acetalization and Wacker‐type oxidation of terminal alkenes normally proceed with Markovnikov selectivity to afford internally oxyfunctionalized compounds, such as internal acetals and ketones. Thus, the realization of anti‐Markovnikov (AM) selectivity in these reactions is challenging. This account focuses on our recent development of Pd‐catalyzed AM oxidation of terminal alkenes (mainly styrenes and aliphatic alkenes), that is, oxidative acetalization (oxidation to terminal acetals) and Wacker‐type oxidation (oxidation to aldehydes). The key factors that enhance the yield and AM selectivity of the products found in our studies are: 1) the steric bulkiness of the oxygen nucleophiles that attack on the coordinated alkenes, 2) the electron‐deficient cyclic alkenes as additives that withdraw electrons from Pd, 3) the slow addition of substrates in the case of the aliphatic alkenes, which suppresses the isomerization of the terminal alkenes into internal alkenes, and 4) the halogen directing groups in the case of aliphatic alkenes.

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tert-Butyl Nitrite: Organic Redox Cocatalyst for Aerobic Aldehyde-Selective Wacker–Tsuji Oxidation

Cited by 68 publications

References 37 publications

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

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

Reverse Polarity Reductive Functionalization of Tertiary Amides via a Dual Iridium-Catalyzed Hydrosilylation and Single Electron Transfer Strategy

Realization of Anti‐Markovnikov Selectivity in Pd‐Catalyzed Oxidative Acetalization and Wacker‐Type Oxidation of Terminal Alkenes

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