Cutting edge of diphenyl phosphorazidate (DPPA) as a synthetic reagent – A fifty-year odyssey

Shioiri, Takayuki; Ishihara, Kotaro; Matsugi, Masato

doi:10.1039/d2qo00403h

Cited by 11 publications

(6 citation statements)

References 137 publications

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“…As shown in Scheme 1, monomers were synthesized through the nucleophilic addition between the styryl Grignard reagent and benzophenone with different substitutions, followed by further azidation of the resulting alkoxide in the presence of diphenyl phosphate azide (DPPA, (C 6 H 5 O) 2 P(O)N 3 ) as azide source in one pot. 63,64 This synthetic method converts ketones into azide-containing monomers directly in one pot, where the separation of intermediate alcohols or alcohol derivatives is not required.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…To verify the above hypothesis, vinyltriphenylmethyl azide-containing monomers were synthesized with different substitutions, including vinyltriphenylmethyl azide (VTPMA), vinylfluorotriphenylmethyl azide (VFTPMA), vinyldifluorotriphenylmethyl azide (V2FTPMA), vinylchlorotriphenylmethyl azide (VCTPMA), and vinylchlorotriphenylmethyl azide (V2CTPMA). As shown in Scheme , monomers were synthesized through the nucleophilic addition between the styryl Grignard reagent and benzophenone with different substitutions, followed by further azidation of the resulting alkoxide in the presence of diphenyl phosphate azide (DPPA, (C 6 H 5 O) 2 P(O)N 3 ) as azide source in one pot. , This synthetic method converts ketones into azide-containing monomers directly in one pot, where the separation of intermediate alcohols or alcohol derivatives is not required.…”

Section: Resultsmentioning

confidence: 99%

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Radical Polymerization-Induced Nontraditional Intrinsic Luminescence of Triphenylmethyl Azide-Containing Polymers

Han

Cai

et al. 2023

Macromolecules

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Nontraditional intrinsic luminescent (NTIL) polymers are an emerging class of luminescent polymer materials, and the molecular design of novel NTIL polymer luminogens is highly desirable. Here, a series of aggregation-induced emission (AIE) type NTIL polymers, including polytriphenylmethyl azide, polyfluorotriphenylmethyl azide, polydifluorotriphenylmethyl azide, polychlorotriphenylmethyl azide, and polydichlorotriphenylmethyl azide, have been synthesized through reversible addition–fragmentation chain transfer (RAFT) polymerization-induced emission (PIE) successfully. Investigations reveal that the triphenylmethyl azide moiety is a novel PIE luminogen for the molecular design of NTIL polymers, where triphenylmethyl azide is nonemissive but triphenylmethyl azide-containing polymers are emissive. Further applications were performed for explosive detection and luminescence energy transfer applications. Therefore, this work expands the molecular structure library of NTIL and AIE materials that might cause inspirations in different fields including click chemistry, living polymerization, PIE, AIE, and NTIL.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Radical Polymerization-Induced Nontraditional Intrinsic Luminescence of Triphenylmethyl Azide-Containing Polymers

Han

Cai

et al. 2023

Macromolecules

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“…The reaction succeeded with the formation of anilide 13 in 95 % yield. Finally, N ‐protected amino acid 9 was involved in the modified Curtius reaction through the treatment with allyl alcohol and diphenyl phosphoroyl azide (DPPA) [42] to give the corresponding allyl carbamate 14 in 88 % yield (Scheme 6).…”

Section: Resultsmentioning

confidence: 99%

Expedient Synthesis of 6‐Functionalized Azabicyclo[4.1.0]heptane Derivatives

Omelian,

Ostapchuk,

Dobrydnev

et al. 2023

ChemistrySelect

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An efficient approach to the synthesis of previously unreported azabicyclo[4.1.0]heptane‐derived building blocks is reported following the divergent strategy. The common synthetic precursor – tert‐butyl 6‐(hydroxymethyl)‐3‐azabicyclo[4.1.0]heptane‐3‐carboxylate was obtained in four steps with 38 % overall yield and was involved in short reaction sequences (1–3 steps) to provide the target bifunctional derivatives, including novel bicyclic N‐Boc protected γ‐amino acid. The described compounds are interesting in terms of lead‐likeness concepts, according to which the rigid 3D‐shaped and sp3‐enriched frameworks are among the most promising entry points for drug discovery projects.

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“…The obtained amino acid derivatives were transformed into monoprotected diamines using a well-established modified Curtius rearrangement protocol. [29] In particular, reaction of acids 9 f-i with diphenyl phosphoroyl azide (DPPA) followed by decomposition of the intermediate isocyanate with conc aq HCl resulted in monoprotected diamines 10 f-i (Scheme 3). Further protection of the primary amine moiety and catalytic debenzylation resulted in mono-N-Boc protected diamines 12 f-i in 56-70 % yield over two steps.…”

Section: Synthesismentioning

confidence: 99%

gem‐Difluoro‐3‐azabicyclo[3.n.1]alkanes and Their Derivatives – Bicyclic Fluorinated Piperidine Isosteres for Drug Discovery

Kihakh,

Melnykov,

Bilenko

et al. 2023

Eur J Org Chem

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An approach to gem‐difluoro‐3‐azabicyclo[3.n.1]alkane‐ derived building blocks via double‐Mannich addition – deoxofluorination sequence is described. The scope of the method was demonstrated for a series of saturated (hetero)cyclic ketones or ketoesters (including five‐ to seven‐membered cycloalkane derivatives and N‐, O‐, S‐containing saturated heterocycles). Further transformations of functional groups produced a number of bifunctionalized difluorinated building blocks, namely, N‐protected aminoacids, mono‐N‐Boc‐protected diamines, and unprotected aminoalcohols in good to excellent overall yields. For the azabicyclo[3.3.1]alkane series, a potential for isosteric replacements is demonstrated by evaluation of the key physicochemical properties (i.e., pKa(H) and LogP).

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Cutting edge of diphenyl phosphorazidate (DPPA) as a synthetic reagent – A fifty-year odyssey

Abstract: Recent advances of diphenyl phosphorazidate (DPPA) as a versatile synthetic reagent was described. It works as an azide anion equivalent, 1,3-dipole, an electrophile, and nitrene. Thus it can be conveniently...

Cited by 11 publications

References 137 publications

Radical Polymerization-Induced Nontraditional Intrinsic Luminescence of Triphenylmethyl Azide-Containing Polymers

Radical Polymerization-Induced Nontraditional Intrinsic Luminescence of Triphenylmethyl Azide-Containing Polymers

Expedient Synthesis of 6‐Functionalized Azabicyclo[4.1.0]heptane Derivatives

gem‐Difluoro‐3‐azabicyclo[3.n.1]alkanes and Their Derivatives – Bicyclic Fluorinated Piperidine Isosteres for Drug Discovery

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