Synthesis of spirocyclic scaffolds using hypervalent iodine reagents

Singh, Fateh V.; Kole, Priyanka B.; Mangaonkar, Saeesh R.; Shetgaonkar, Samata E.

doi:10.3762/bjoc.14.152

Cited by 62 publications

(26 citation statements)

References 140 publications

(106 reference statements)

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“…They are especially useful for constructing spirocyclic compounds by oxidative dearomative cyclization of phenols, and the resulting spirocyclic cyclohexadienones can easily be further functionalized . So far, various spirocyclization reactions have been explored by using intramolecular pendent nitrogen and/or oxygen nucleophiles, such as amine, amide, alcohol and carboxylic acid (Scheme A) . However, to our knowledge, oxidative dearomative spirocyclization using guanidine as a nucleophile has not yet been reported.…”

Section: Figurementioning

confidence: 99%

“…[9] So far, various spirocyclization reactions have been explored by using intramolecular pendent nitrogen and/or oxygen nucleophiles, such as amine, amide, alcohol and carboxylic acid (Scheme 1A). [10,11] However, to our knowledge, oxidative dearomative spirocyclization using guanidine as a nucleophile has not yet been reported. Herein, we describe a novel strategy to access the spirocyclic guanidine structure by oxidative dearomative cyclization of guanidino phenols in the presence of a hypervalent iodine reagent (Scheme 1B).…”

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confidence: 98%

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Synthesis of Spiroguanidine Derivatives by Dearomative Oxidative Cyclization using Hypervalent Iodine Reagent

et al. 2020

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Section: Figurementioning

confidence: 99%

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confidence: 98%

Synthesis of Spiroguanidine Derivatives by Dearomative Oxidative Cyclization using Hypervalent Iodine Reagent

et al. 2020

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“…have been utilized with great success in aplethora of oxidative coupling reactions [1] and in natural product synthesis. [2] In related enantioselective processes,achiral aryl iodide precursor can be used in catalytic amounts in combination with aterminal co-oxidant to generate achiral hypervalent iodine compound in situ. This chiral oxidant is subsequently capable of transferring its chirality onto the desired coupling products through diastereotopic transition states in the key oxidative C-X bond forming step.…”

Section: Hypervalentiodinecompoundsareversatileoxidantswhichmentioning

confidence: 99%

A Triazole‐Substituted Aryl Iodide with Omnipotent Reactivity in Enantioselective Oxidations

Abazid

Nachtsheim

2019

Angewandte Chemie

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Aw idely applicable triazole-substituted chiral aryl iodide is described as catalyst for enantioselective oxidation reactions.The introduction of asubstituent in ortho-position to the iodide is key for its high reactivity and selectivity.B esides ar obust and modular synthesis,t he main advantage of this catalyst is the excellent performance in ap lethora of mechanistically diverse enantioselective transformations,s uch as spirocyclizations,p henol dearomatizations, a-oxygenations, and oxidative rearrangements.D FT-calculations of in situ generated [hydroxy(tosyloxy)iodo]arene isomers give an initial rational for the observed reactivity.Hypervalentiodinecompoundsareversatileoxidantswhich have been utilized with great success in aplethora of oxidative coupling reactions [1] and in natural product synthesis. [2] In related enantioselective processes,achiral aryl iodide precursor can be used in catalytic amounts in combination with aterminal co-oxidant to generate achiral hypervalent iodine compound in situ. This chiral oxidant is subsequently capable of transferring its chirality onto the desired coupling products through diastereotopic transition states in the key oxidative C-X bond forming step. [3] Since the discovery of the first enantioselective transformation catalyzed by ac hiral aryl iodide in 2007 by Wirth and co-workers, [4] more than ad ozen highly diverse C1-and C2-symmetric chiral aryl iodides have been developed. [5] Successful catalysts,s uch as 1-4 ( Figure 1), usually show ag ood reactivity and selectivity in only one distinct class of oxidative transformation. So far there is no omnipotent chiral aryl iodide available that performs well throughout the most important oxidative transformations and hence can be seen as broadly applicable catalyst for iodane-based enantioselective couplings.Our group is heavily interested in the development of N-heterocycle-stabilized iodanes (NHIs) as an ew class of stable and at the same time highly reactive hypervalent iodine compounds. [6, 7] With the aim to design novel chiral aryl iodides which are robust to synthesize in amodular sequence and show ag ood performance throughout adiverse range of enantioselective oxidations,w erecently developed the novel triazole-substituted aryl iodide 5 ( Figure 2) and evaluated its reactivity in the Kita-spirocyclization of 1-naphthols. [8] Even though this "first-generation" catalyst gave the so far highest enantioselectivities in direct comparison to other C1-symmetric aryl iodides for this reaction, reactivities were low.W ell-established C2-symmetric aryl iodides,s uch as spirobiindanes developed by Kita or resorcinol ethers 1 developed by Uyanik and Ishihara, showed significantly higher stereoinduction and yielded the desired chiral lactones in better yields. [9] Due to the promising initial results with catalyst 5 and its highly modular and robust synthesis,w e further developed "second-generation" triazole catalysts 6 ( Figure 2) bearing as imple ortho-modification at the aryl iodide.W et herefore synthesized orth...

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“…Intramolecular ipso ‐annulation has received considerable attention in organic synthesis, for efficient carbon–nitrogen (C‐N) bond formation in single operation by hypervalent iodine(III) reagents. In this regard recently Reddy et al focussed on review on ipso ‐Cyclization for synthesis of spirocyclohexadienones, by using hypervalent iodine(III) reagents or organo iodoarenes for C‐N bond formations , , , , , …”

Section: Miscellaneousmentioning

confidence: 99%

Recent Advances in Intramolecular Metal‐Free Oxidative C–H Bond Aminations Using Hypervalent Iodine(III) Reagents

et al. 2019

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Hypervalent iodine chemistry is a rapidly growing area of research with tremendous impact on synthetic chemistry in the past years. A rich and diverse chemistry is now available for reactions using hypervalent iodine reagents, as metal‐free, ecofriendly reagents and the advent of new reactions will be of large benefit to researchers working in the area of selective synthesis. In this review article, we emphasize the usage of hypervalent iodine(III) reagents for metal‐free intramolecular oxidative C–N bond formation/annulation to synthesize wide range of N‐heterocycles in organic synthesis. The functionalization of C–H bonds through the involvement of sp‐, sp2‐, and sp3‐hybridized carbon atoms for cyclizations is discussed in detail.

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Synthesis of spirocyclic scaffolds using hypervalent iodine reagents

Cited by 62 publications

References 140 publications

Synthesis of Spiroguanidine Derivatives by Dearomative Oxidative Cyclization using Hypervalent Iodine Reagent

Synthesis of Spiroguanidine Derivatives by Dearomative Oxidative Cyclization using Hypervalent Iodine Reagent

A Triazole‐Substituted Aryl Iodide with Omnipotent Reactivity in Enantioselective Oxidations

Recent Advances in Intramolecular Metal‐Free Oxidative C–H Bond Aminations Using Hypervalent Iodine(III) Reagents

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