Organoiodine‐Catalyzed Enantioselective Alkoxylation/Oxidative Rearrangement of Allylic Alcohols

Zhang, Dongyang; Zhang, Ying; Wu, Hua; Gong, Liu‐Zhu

doi:10.1002/anie.201903007

Cited by 40 publications

(27 citation statements)

References 59 publications

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“…Apart from oxygenations, hypervalent iodine compounds can be applied efficiently in enantioselective rearrangements . Very recently, Gong and co‐workers developed the oxidative rearrangement of allylic alcohols to β‐oxygenated ketones with the lactic‐acid‐derived catalyst 1 c . We utilized this useful reaction as another benchmark for 6 c (Scheme d).…”

Section: Figurementioning

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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Section: Figurementioning

confidence: 99%

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

Abazid

Nachtsheim

2019

Angewandte Chemie

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“…At the conclusion of our study, we were curious if catalysis could be achieved by pairing iodobenzene with a superstoichiometric oxidant. Oxidative catalytic processes using an iodine catalyst have emerged recently as a powerful way to create new bonds through the dearomatization of electron-rich arenes. , While phenols and aromatic ethers are common substrates, the development of I(III)-catalyzed oxidative methods of anilines remains nascent and requires a strong electron-withdrawing group on nitrogen for C–N bond formation . In 2011, Antonchick and co-workers reported that biaryl acetimides could be transformed into N -acetyl carbazoles using a diiodobiaryl catalyst and acetic peroxide as the oxidant (Scheme ).…”

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confidence: 99%

I(III)-Catalyzed Oxidative Cyclization–Migration Tandem Reactions of Unactivated Anilines

et al. 2020

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An I(III)-catalyzed oxidative cyclization–migration tandem reaction using Selectfluor as the oxidant was developed that converts unactivated anilines into 3H-indoles is reported herein. The reaction requires as little as 1 mol % of the iodocatalyst and is mild, tolerating pyridine and thiophene functional groups, and the dependence of the diastereoselectivity of the process on the identity of the iodoarene or iodoalkane precatalyst suggests that the catalyst is present for the stereochemical determining C–N bond forming step.

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“…In contrast, NHIA 10a showed a high reactivity yielding the desired lactone 14 in 91% and still in good yield of 80% with only 10 mol% catalyst loading. Finally, the oxidative rearrangement of allylic alcohol 15 [32] (Scheme 2 -c) was investigated.…”

Section: Resultsmentioning

confidence: 99%

Evolution of N-Heterocycle-substituted Iodoarenes (NHIAs) to efficient Organocatalysts in Iodine(I/III)-mediated Oxidative Transformations

Boelke¹,

Nachtsheim

2019

Preprint

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We herein describe the development of <i>N</i>-heterocycle-stabilized iodoarenes (NHAIs) as oxidation catalysts for oxidative C-X-bond forming reactions. Modification of the N-heterocycle as stabilizing donor in combination with an additional ortho-methoxylation of the iodoarene finally gives organocatalysts that can be applied in the alpha-oxytosylation of ketones even with catalyst loadings as low as 1 mol%. <br>

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Organoiodine‐Catalyzed Enantioselective Alkoxylation/Oxidative Rearrangement of Allylic Alcohols

Cited by 40 publications

References 59 publications

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

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

I(III)-Catalyzed Oxidative Cyclization–Migration Tandem Reactions of Unactivated Anilines

Evolution of N-Heterocycle-substituted Iodoarenes (NHIAs) to efficient Organocatalysts in Iodine(I/III)-mediated Oxidative Transformations

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