Silver-Catalyzed Oxidative Cyclization of Propargylamide-Substituted Indoles: Synthesis of Phosphorated Indoloazepinones Derivatives

Hua, Hui‐Liang; Zhang, Bo‐Sheng; He, Yu‐Tao; Qiu, Yi‐Feng; Wu, Xin‐Xing; Xu, Peng‐Fei; Liang, Yong‐Min

doi:10.1021/acs.orglett.5b03329

Cited by 43 publications

(17 citation statements)

References 64 publications

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“…On the basis of the results obtained here and previous reports,, a plausible mechanism for the oxidative radical process is depicted in Figure . Firstly, diphenylphosphine oxide underwent a single electron transfer with Ag(I) salt to genertate the radical cation I and Ag(0) ,. Then, the phosphorus radical II was obtained by the loss of a proton.…”

Section: Methodssupporting

confidence: 64%

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Silver‐Catalyzed Carbon‐Phosphorus Functionalization for Polyheterocycle Formation

et al. 2017

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Polyheterocycle construction with high diastereoselectivity by utilizing ar adical process is still problematic. In this communication,asilvercatalyzed carbon-phosphorus functionalization for polyheterocycle formation is described that furnishes good diastereoselectivity.V arious substituted 1-(1H-indol-1-yl)-3-phenylprop-2-en-1-ones and phosphineo xides were suitable for this transformation. This work avoids the installationo fd irect functional groups and thus makes full use of shorter and more efficient synthetic processes. Preliminary mechanistic investigations indicate that phosphorus radicals are involved by attacking the a-position of a,b-unsaturated carbonyl compounds to generate the desired products.Polyheterocycles are ubiquitous structural motifs found in natural productsa nd pharmaceuticals and also serve as valuable synthetic intermediates in the preparation of functional materials. [1,2] Owing to the extended heteroaromatic conjugated systems,p olyheterocycles and their derivatives are attracting tremendous attention directed to the developmento fs imple and efficient methodologies for theirc onstruction. [3,4] In the past, substantial advances were directedtoward efficient methods for these compounds by transition metal-catalyzed cyclization/functionalization approaches. Also,i th as emerged as one of the most importants ynthetic methodsb ecause of its particulare fficiency. [5] However, these approachess ufferf rom elaborately designed substrates and low functional group compatibility of polyheterocycles,thereby limiting their wide applications in organic chemistry research and industry.T hus,t he development of simple synthetic methods in which the polyheterocycle unit is constructed simultaneously via ar adical cyclization featuring facile operation and easily accessible starting materials remains relatively exploited but still challenging.Carbon-phosphorus functionalization has become one of the most important synthetic methodsf or the formation of phosphorus-containing compounds because many natural products or biomolecules contain these modified units in their structures.Atransition metal-catalyzed functionalization of the C-P bond by oxidative cross-coupling between C-H and P-H bonds willa void the installation of direct functional groups andt hus make full use of shorter and more efficient synthetic routes. [6][7][8][9] Despite considerable progress in the field, there still remain great challenges in oxidative C-H/P-H cross-coupling, [10][11][12][13] especially for obtainingg oodd iastereoselectivity in the polyheterocyclest hrough carbon-phosphorus functionalization. It is wellk nown that the phosphorus radical is electrophilic on generation from the oxidation of P-H bonds.W ee nvisioned that the phosphorus radical triggeredb yas ilver catalyst would easily attack the a-position of a,b-unsaturated carbonyl compounds owingt oi ts higher electrond ensity.T hereby an acarbon radical is formed by the intramolecular radical addition.L astly,t he active species is transformed into the polyheter...

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Section: Methodssupporting

confidence: 64%

“…However, exposure of [Ph 2 P(O)Ag] complex (10 mol%) and 1a did afford the desired product in 73% yield (Scheme c). It was demonstrated that the P‐radical was generated from Ph 2 P(O)H in the presence of silver salt and the [Ph 2 P(O)Ag] complex was not an active intermediate in our reaction , …”

Section: Methodsmentioning

confidence: 80%

Silver‐Catalyzed Carbon‐Phosphorus Functionalization for Polyheterocycle Formation

et al. 2017

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“…An Ag(I)‐catalyzed oxidative radical cyclization of alkynes with phosphine oxides toward seven‐membered phosphorylated nitrogen heterocycles has been disclosed by Liang et al. in 2016 . In the presence of 10 mol% of AgOAc along with Zn(NO 3 ) 2 ⋅6 H 2 O, 2‐ or 3‐propargylamide‐substituted indoles 548 or 549 underwent a tandem phosphinoylation/cyclization/oxidation and aromatization sequence to afford indoloazepinone derivatives 550 or 551 that are common structural motifs in many natural products (Scheme ).…”

Section: Reactions Involving Heterocyclic Ring Formationmentioning

confidence: 99%

Recent Advances in the Construction of Phosphorus‐Substituted Heterocycles, 2009–2019

2020

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Scheme 20. Phosphonation of pyridinones.Scheme 21. CuI-catalyzed phosphoramidate formation.Scheme22. Phosphonation of coumarin and quinolinone.Scheme23. Silver(I)-catalyzed phosphonation of coumarins. Scheme 33. Electrochemical C(sp 2 )ÀHphosphonation of quinoxaline-2(1H)-ones. Scheme 39. Phosphorylation of quinoxaline-2(1 H)-ones. Scheme40. Autoxidative phosphorylation of quinoxalines. Scheme 41. DTBP-mediated formation of phosphonated benzothiazoles. Scheme42. Phosphonation of imidazole[2,1-b]thiazoles.Scheme 47. Copper(I)-catalyzedp hosphonationo fN-iminoisoquinolinium ylides. Scheme48. Aerobic phosphonationofC ( sp 3 ) À Hbonds. Scheme 49. Copper(II)/PBQ-catalyzed phosphorylation of 3,4-dihydro-1,4-benzoxazin-2-ones. Scheme 87. Asymmetric exo-selective [3+ +2] cycloaddition to afford phosphorus-substituted pyrrolidines. Scheme 95. Cascade condensation/cyclization to phosphonylated thienopyridines. Scheme 96. S N Ar'-involved cascade reactions to phosphonylated oxygenorn itrogen heterocycles.Scheme 97. Manganese(III)-mediated synthesis of 3-phosphonyldihydrofuransfrom b-ketophosphonates.Scheme98. Cyclization to phosphonated isochromenes.Scheme 121. Asymmetric [4+ +2] cycloaddition of b,g-unsaturated a-ketophosphonates.

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“…Upon single electron transfer and consequent deprotonation, the final phosphorated indoloazepinone 432 a is formed (Scheme 112). [132] …”

Section: Metamorphosis Of Heteroarene‐tethered Propargyl Amidesmentioning

confidence: 99%

“…This oxidative cyclization rection displayedb ifunctionlization of alkyne with diphenylphosphine oxidesv ia ar adical mechanism constructing an ew 7-membered ring system.A uthorsd escribed the plausible mechanism by taking account the initial formation of P-radical I generated from the diphenylphosphine oxide by Ag I salt which upon selective addition to the alkyne generates av inyl radical II.S ubsequent7 -endo-trig cyclization of II generates intermediate III.U pon single electron transfer and consequent deprotonation, the final phosphorated indoloazepinone 432 a is formed( Scheme1 12). [132] Scheme107. Intramolecular azavinyl carbene-triggeredr earrangement of furans.…”

Section: Metamorphosis Of Heteroarene-tethered Propargyl Amidesmentioning

confidence: 99%

Heteroarene‐tethered Functionalized Alkyne Metamorphosis

Bag

Sawant

2020

Chemistry A European J

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Heteroarene-tethered functionalized alkynes are multipotents ynthons in organic chemistry.T his detailed Review described herein offers at horough discussion of the metamorphosis of heteroarene-tethered functionalized alkynes, an area which has earned much attention over the past decade in the straightforward synthesis of architecturally complex heterocyclics caffolds in atom and step economic manner.D epending upon the variety of functionalized al-kynes, this Review is divided into multiple sections. Amongst the vast array of synthetic transformations covered, dearomatizings pirocyclizations and cascades pirocyclization/rearrangementa re of great interest. Synthetic transformations involving the heteroarene-tethered functionalized alkynes with scope, challenges, limitations, mechanism, their application in the total synthesis of natural products and future perceptionsa re surveyed. [a] D. Bag, Prof.

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Silver-Catalyzed Oxidative Cyclization of Propargylamide-Substituted Indoles: Synthesis of Phosphorated Indoloazepinones Derivatives

Cited by 43 publications

References 64 publications

Silver‐Catalyzed Carbon‐Phosphorus Functionalization for Polyheterocycle Formation

Silver‐Catalyzed Carbon‐Phosphorus Functionalization for Polyheterocycle Formation

Recent Advances in the Construction of Phosphorus‐Substituted Heterocycles, 2009–2019

Heteroarene‐tethered Functionalized Alkyne Metamorphosis

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