Reaction of saturated organic compounds with acetyl and trifluoroacetyl nitrate

Bach, Robert D.; Taaffee, Thomas H.; Holubka, Joseph W.

doi:10.1021/jo01305a013

Cited by 9 publications

(4 citation statements)

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“…This corroborates earlier investigations with nitronium tetrafluoroborate as activating agent . When the corresponding nitronium acetate or trifluoroacetate were used, the acetic or trifluoracetic esters were formed …”

Section: General Transformations: Applications In Synthesissupporting

confidence: 91%

Alkyliodines in High Oxidation State: Enhanced Synthetic Possibilities and Accelerated Catalyst Turn‐Over

Bosnidou

Muñiz

2019

Chemistry A European J

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In contrast to aryliodine(III) compounds, which have matured into a particularly attractive class of oxidants in modern synthesis, the synthetic potential of related alkyliodine(III) derivatives has remained widely underestimated. This is surprising since several unique synthetic possibilities arise directly from the low stability of their central carbon–iodine bond. In this respect, these high‐oxidation‐state iodine compounds resemble environmentally benign variants of the prominent metal counterparts such as those derived from palladium, nickel and copper. This Concept article summarizes the general reactivity trends in alkyliodine(III) chemistry and discusses selected examples of their strategic use as highly reactive, transient species in organic synthesis and homogeneous catalysis.

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Section: General Transformations: Applications In Synthesissupporting

confidence: 91%

Alkyliodines in High Oxidation State: Enhanced Synthetic Possibilities and Accelerated Catalyst Turn‐Over

Bosnidou

Muñiz

2019

Chemistry A European J

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“…The direct C–H functionalization of nonactivated alkanes is still relatively scarce due to their intrinsic low reactivity. Acyloxylation of C(sp 3 )–H bonds in alkanes was achieved with [Au]/PIDA, Co(OAc) 2 /I 2 /NHPI/O 2 /HNO 3 , H 2 O 2 /TFA, Selectfluor/CuBr 2 /pentanenitrile, TFAN/TFA, RuCl 3 /AcOOH/TFA, Fe(III)/O 2 /TFA/ hv , and [Mn]/H 2 O 2 . , In some cases, it was difficult to avoid overoxidation of the product, which led to allyl esters (CuTPP/DTBP, Cu(OAc) 2 / TBHP, [(BPI)CuCl]/ DTBP, and CuO/DTBP).…”

Section: Resultsmentioning

confidence: 99%

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

et al. 2023

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The reaction of Ni(II) acetate with diacyl peroxides produces high-valence Ni-species capable of catalytic oxidative acyloxylation of C(sp3)–H bonds in ethers, ketones, and alkanes. The desired esters were obtained in 20–82% yields. Computational analysis suggests that activation of the peroxide moiety produces a dynamically interconverting mixture of catalytic Ni-species in the formal Ni(III) state. Remarkably, in these species, coordination of the RCO2 group at Ni preserves radical character at the carboxylate moiety (i.e., carboxylate radical acts as an “L-ligand”), so the latter can induce fast C–H abstraction. The spirocyclopropyl moiety prevents premature radical decarboxylation via a combination of hybridization factors and stereoelectronic effects. A variety of viable C–H activation patterns were identified experimentally and computationally.

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“…140 It is of note that acyl nitrate can react with saturated aliphatic compounds, although this is not a nitration reaction. 141 In the presence of chlorotrimethylsilane/acetyl nitrate mixture, nitryl chloride can be generated and used in the one-pot synthesis of gem-chloronitro compounds from oximes. 142 Besides the above-discussed application, acyl nitrates are also used in the oxidation of sulfides 143 and tertiary amines.…”

Section: Special Topic Synthesismentioning

confidence: 99%

Organic Nitrating Reagents

Patra¹,

Mosiagin²,

Katayev³

et al. 2022

Synthesis

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Nitro compounds are vital raw chemicals that are widely used in academic laboratories and industries for the preparation of various drugs, agrochemicals, and materials. Thus, nitrating reactions are of great importance for chemists and are even taught in schools as one of the fundamental transformations in organic synthesis. Since the discovery of the first nitrating reactions in the 19th century, progress in this field has been constant. Yet, for many years the classical electrophilic nitration approach using a mixture of strong mineral acids dominated the field. However, in recent decades, the attention of researchers has focused on new reactivity and new reagents that can provide access to nitro compounds in a practical and straightforward way under mild reaction conditions. Organic nitrating reagents have played a special role in this field since they have enhanced reactivity. They also allow nitration to be carried out in an ecofriendly and sustainable manner. This review examines the development and application of organic nitrating reagents.1 Introduction2 Organic Nitrating Reagents2.1 Alkyl Nitrites2.2 Nitroalkanes2.3 Alkyl Nitrates2.4 N-Nitroamides2.5 N-Nitropyrazole2.6 N-Nitropyridinium Salts3 Organic Nitrating Reagents Generated In Situ3.1 Acyl Nitrates3.2 Trimethylsilyl Nitrate3.3 Nitro Onium Salts4 Organic Nitronium Salts5 Organic Nitrates and Nitrites5.1 Ammonium Nitrates5.2 Heteroarylium Nitrates5.3 Other Organic Nitrates5.4 Organic Nitrites6 Conclusion and Outlook

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Reaction of saturated organic compounds with acetyl and trifluoroacetyl nitrate

Cited by 9 publications

References 0 publications

Alkyliodines in High Oxidation State: Enhanced Synthetic Possibilities and Accelerated Catalyst Turn‐Over

Alkyliodines in High Oxidation State: Enhanced Synthetic Possibilities and Accelerated Catalyst Turn‐Over

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

Organic Nitrating Reagents

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Reaction of saturated organic compounds with acetyl and trifluoroacetyl nitrate

Cited by 9 publications

References 0 publications

Alkyliodines in High Oxidation State: Enhanced Synthetic Possibilities and Accelerated Catalyst Turn‐Over

Alkyliodines in High Oxidation State: Enhanced Synthetic Possibilities and Accelerated Catalyst Turn‐Over

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp3)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

Organic Nitrating Reagents

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Product

Resources

About

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides