Dearomatization of aryl sulfoxides: a switch between mono- and dual-difluoroalkylation

Huang, Xin; Zhang, Yage; Liang, Weijian; Zhang, Zuo‐Feng; Zhan, Yaling; Kong, Lichun; Peng, Bo

doi:10.1039/d0sc00244e

Cited by 32 publications

(13 citation statements)

References 60 publications

(4 reference statements)

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“…[13] Further studies revealed that the choice of bases was also critical to the reaction. Pyridine derivatives were more effective than aliphatic tertiary amines (entries [10][11][12][13]. Further optimization of the reaction temperatures and reaction times identified the best conditions giving 5aa in 71 %yield (entry 16).…”

Section: Resultsmentioning

confidence: 99%

Morita–Baylis–Hillman‐Type [3,3]‐Rearrangement: Switching fromZ‐ toE‐Selective α‐Arylation by New Rearrangement Partners

et al. 2021

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a-aryl a,b-unsaturated carbonyls represent an important class of derivatizable synthetic intermediates,h owever,the synthesis of such compounds still remains achallenge. Recently,weshowcased anovel Z-selective a-arylation of a,bunsaturated nitriles with aryl sulfoxides via [3,3]-rearrangement involving an Morita-Baylis-Hillman (MBH) process. Herein, we demonstrate the feasibility of reversing the stereoselectivity of such MBH-type [3,3]-rearrangement by switching to an ew pair of rearrangement partners consisting of aryl iodanes and a,b-unsaturated oxazolines.A saresult, the two protocols complement each other in approaching E-or Z-aaryl a,b-unsaturated carbonyl derivatives.M echanistic studies reveal apossible reaction pathway and provide an explanation for the opposite stereoselectivities.

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Section: Resultsmentioning

confidence: 99%

Morita–Baylis–Hillman‐Type [3,3]‐Rearrangement: Switching fromZ‐ toE‐Selective α‐Arylation by New Rearrangement Partners

et al. 2021

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“…In 2020, Peng and co-workers reported a dearomatization strategy involving aryl sulfoxides 49a and the difluoroenol silyl ether (DFESE) 49b, as a highly effective nucleophilic rearrangement partner, to generate dearomatized products 49c and 49d (Scheme 49). 86 This protocol represents the first example of a dearomatization reaction in aryl sulfoxide chemistry. Depending on the electrophilic activator employed (TFAA or Tf 2 O), this transformation delivers dearomatized products 49c and 49d possessing either mono-or bis-difluoroalkyl groups.…”

Section: Review Synthesismentioning

confidence: 99%

Triflic Anhydride (Tf2O)-Activated Transformations of Amides, Sulfoxides and Phosphorus Oxides via Nucleophilic Trapping

Huang

Kang

2021

Synthesis

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Trifluoromethanesulfonic anhydride (Tf2O) has found a wide range of applications in synthetic organic chemistry as a strong electrophilic activator leading to the transient generation of a triflate intermediate. This versatile triflate intermediate undergoes nucleophilic trapping with diverse nucleophiles to yield novel compounds. In this review, we describe the features and applications of triflic anhydride in organic synthesis reported in the past decade, especially in amide, sulfoxide, and phosphorus oxide chemistry through electrophilic activation. A plausible mechanistic pathway of each important reaction is also discussed.

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“…1a , product IV and VI ) 39 . Recently, several excellent studies aiming to address the activity issues were achieved by developing new catalytic model 8 , 32 or using energetic intermediates and substrates 37 , 38 , 40 , 41 . For example, Peng group disclosed a dearomative dual functionalization of aryl iodanes by integration a iodonio-Claisen rearrangement with a subsequent nucleophilic interception of the dearomative intermediate (Fig.…”

Section: Introductionmentioning

confidence: 99%

Divergent synthesis of benzazepines and bridged polycycloalkanones via dearomative rearrangement

et al. 2022

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The dearomative functionalization of aromatic compounds represents a fascinating but challenging transformation, as it typically needs to overcome a great kinetic barrier. Here, a catalyst-free dearomative rearrangement of o-nitrophenyl alkyne is successfully established by leveraging the remote oxygen transposition and a weak N-O bond acceleration. This reaction features high atom-, step- and redox-economy, which provides a divergent entry to a series of biologically important benzazepines and bridged polycycloalkanones. The reaction is proposed to proceed through a tandem oxygen transfer cyclization/(3 + 2) cycloaddition/(homo-)hetero-Claisen rearrangement reaction. The resulting polycyclic system is richly decorated with transformable functionalities, such as carbonyl, imine and diene, which enables diversity-oriented synthesis of alkaloid-like polycyclic framework.

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Dearomatization of aryl sulfoxides: a switch between mono- and dual-difluoroalkylation

Abstract: Herein we describe the dearomatization of aryl sulfoxides with difluoroenol silyl ether (DFESE) using a rearrangement/addition protocol.

Cited by 32 publications

References 60 publications

Morita–Baylis–Hillman‐Type [3,3]‐Rearrangement: Switching fromZ‐ toE‐Selective α‐Arylation by New Rearrangement Partners

Morita–Baylis–Hillman‐Type [3,3]‐Rearrangement: Switching fromZ‐ toE‐Selective α‐Arylation by New Rearrangement Partners

Triflic Anhydride (Tf2O)-Activated Transformations of Amides, Sulfoxides and Phosphorus Oxides via Nucleophilic Trapping

Divergent synthesis of benzazepines and bridged polycycloalkanones via dearomative rearrangement

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