Journal ArticleDOI
[3,3]- and [5,5]-Sigmatropic Rearrangements of Aryl Sulfoxides Using An ‘Assembly/Deprotonation’ Technology
Lei Zhang,Mengjie Hu,Bo Peng +2 more
TLDR
In this paper, an ortho-cyanoalkylation of aryl sulfoxides with alkyl nitriles using an assembly/deprotonation protocol is described.Abstract:
The redox-neutral ortho-functionalizations of aryl/heteroaryl sulfoxides via interrupted Pummerer processes have been greatly advanced since its discovery by Kita and Padwa in the early 2000s. In this context, we recently developed an ortho-cyanoalkylation of aryl sulfoxides with alkyl nitriles using an ‘assembly/deprotonation’ protocol. The success of the reaction hinges on the independent control of the electrophilic assembly of both coupling partners and subsequent deprotonation of the in situ generated imine sulfonium intermediates. Further [3,3]-sigmatropic rearrangement of the in situ formed ketenimine sulfonium species furnishes ortho-cyanoalkylated aryl sulfides. More recently, we also applied the ‘assembly/deprotonation’ strategy for the development of the [5,5]-sigmatropic rearrangement of aryl sulfoxides with allyl nitriles that allows for para-cyanoalkylation of aryl sulfoxides. The development of these two reactions is described in this Synpacts article. 1 Background 2 [3,3]-Sigmatropic Rearrangement 3 [5,5]-Sigmatropic Rearrangement 4 Conclusionread more
Citations
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Journal ArticleDOI
Dearomatization of aryl sulfoxides: a switch between mono- and dual-difluoroalkylation
TL;DR: The dearomatization of aryl sulfoxides with difluoroenol silyl ether (DFESE) using a rearrangement/addition protocol to produce dual-difluoroalkylated alicycles is described.
Journal ArticleDOI
Synthesis of ortho-Phenolic Sulfilimines via an Intermolecular Sulfur Atom Transfer Cascade Reaction
TL;DR: This mild reaction enables commercially available thiols to serve as the sulfenylation reagent and generates water as the sole byproduct and has a wide substrate scope and can be conducted on a gram scale with excellent reaction efficiency.
Journal ArticleDOI
Z‐Selective α‐Arylation of α,β‐Unsaturated Nitriles via [3,3]‐Sigmatropic Rearrangement
Mengyuan Chen,Yuchen Liang,Taotao Dong,Weijian Liang,Yanping Liu,Yage Zhang,Xin Huang,Lichun Kong,Zhi-Xiang Wang,Bo Peng +9 more
TL;DR: The reaction was achieved by sequentially treating both coupling partners with electrophilic activator (Tf2O) and base, offering an effective approach to prepare synthetically versatile α-aryl α, β-unsaturated nitriles with Z-selectivity through direct α-C-H arylation of unmodified α,β-uns saturated nitrile.
Journal ArticleDOI
Morita-Baylis-Hillman-Type [3,3]-Rearrangement: Switching from Z- to E-Selective α-Arylation by New Rearrangement Partners.
Lei Zhang,Wangzhen Bao,Yuchen Liang,Wenjing Pan,Dongyang Li,Lichun Kong,Zhi-Xiang Wang,Bo Peng +7 more
TL;DR: In this paper, the authors demonstrate the feasibility of reversing the stereoselectivity of MBH-type [3,3]-rearrangement by switching to a new pair of rearrangement partners consisting of aryl iodanes and α,β-unsaturated oxazolines.
Journal ArticleDOI
Regioselective Difunctionalization of 2,6-Difluorophenols Triggered by Sigmatropic Dearomatization
TL;DR: Regioselective difunctionalization of 2,6-difluorophenols with aryl sulfoxides and nucleophiles has been accomplished using Pummerer-based sigmatropic dearomatization to generate 2,4-cyclohexadienone.
References
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Journal ArticleDOI
Metal-Free CH-CH-Type Cross-Coupling of Arenes and Alkynes Directed by a Multifunctional Sulfoxide Group.
TL;DR: A metal-free CH-CH-type coupling of arenes and alkynes, mediated by a multifunctional sulfoxide directing group, exploits nonprefunctionalized coupling partners, proceeds under mild conditions, is operationally simple, and exhibits high functional group tolerance.
Journal ArticleDOI
Redox-Neutral α-Arylation of Alkyl Nitriles with Aryl Sulfoxides: A Rapid Electrophilic Rearrangement.
Li Shang,Yonghui Chang,Fan Luo,Jia-Ni He,Xin Huang,Lei Zhang,Lichun Kong,Kaixiao Li,Bo Peng,Bo Peng +9 more
TL;DR: NMR studies not only identified a unique, highly unstable sulfonium imine complex but also demonstrated the importance of temperature in the formation and manipulation of this key intermediate.
Journal ArticleDOI
Selective [5,5]-Sigmatropic Rearrangement by Assembly of Aryl Sulfoxides with Allyl Nitriles.
Lei Zhang,Jia-Ni He,Yuchen Liang,Mengjie Hu,Li Shang,Xin Huang,Lichun Kong,Zhi-Xiang Wang,Bo Peng +8 more
TL;DR: A new [5,5]-sigmatropic reaction utilizing readily available aryl sulfoxides and allyl nitriles is described, which features mild reaction conditions, high chemo- and regioselectivity, excellent functional-group compatibility, and broad substrate scope.
Journal ArticleDOI
Metal-Free Cyclopropanol Ring-Opening C(sp 3 )–C(sp 2 ) Cross-Couplings with Aryl Sulfoxides
TL;DR: A metal-free method for formal β-arylation/heteroarylation of ketones through efficient cyclopropanol ring-opening cross-couplings with aryl sulfoxides at room temperature has been developed and shows a broad substrate scope and promising scalability.