- Diiodine-Triethylsilane System: Reduction of N-Sulfonyl Aldimines to N-Alkylsulfonamides
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Because molecular iodine and hydrosilanes are stable to both air and moisture, reactions using these reagents are easy to operate and require mild reaction conditions. Molecular iodine and a hydrosilane were used to reduce N-sulfonyl aldimines to the corr
- Jiang, Jin,Xiao, Lili,Li, Yu-Long
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supporting information
p. 291 - 294
(2020/11/09)
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- Photoredox-mediated mono- And difluorination of remote unactivated methylene C(sp3)-H bonds of N-alkyl sulfonamides
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A photoredox-mediated δ-C(sp3)-H fluorination of sulfonyl-protected primary alkylamines with Selectfluor is developed. The reaction can proceed in excellent monofluorination selectivity for amine substrates without α substituent. For α-substituted substrates, a slightly modified reaction conditions with two rounds of operation gives the δ,δ-difluorination products in good yield. Mechanistic studies suggest SET oxidation of sulfonamide group directly generates the key sulfonamide N radical intermediate, which triggers a 1,5-HAT process to form the δ alkyl radical.
- Deng, Zhiqiang,Zhao, Zhenxiang,He, Gang,Chen, Gong
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supporting information
p. 3631 - 3635
(2021/05/31)
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- Photoinduced site-selective C(sp3)-H chlorination of aliphatic amides
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Herein, we report a new photochemical method for C(sp3)-H chlorination of amides which employs tert-butyl hypochlorite as the chlorinating agent and a household compact fluorescent lamp as the light source. The reaction proceeds via N-heterocyclic carbene SIPr·HCl-promoted N-H chlorination and subsequent photoinduced Hofmann-L?ffler-Freytag chlorine atom transfer. The latter process is facilitated by (diacetoxyiodo)benzene. This protocol exhibits a broad scope and is suitable for site-selective chlorination of methyl hydrogen as well as methylene and methine hydrogen.
- Zhu, Yanshuo,Shi, Jingcheng,Yu, Wei
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supporting information
p. 8899 - 8903
(2020/11/30)
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- Manganese-Catalyzed N-Alkylation of Sulfonamides Using Alcohols
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An efficient manganese-catalyzed N-alkylation of sulfonamides has been developed. This borrowing hydrogen approach employs a well-defined and bench-stable Mn(I) PNP pincer precatalyst, allowing benzylic and simple primary aliphatic alcohols to be employed as alkylating agents. A diverse range of aryl and alkyl sulfonamides undergoes mono-N-alkylation in excellent isolated yields (32 examples, 85% average yield).
- Reed-Berendt, Benjamin G.,Morrill, Louis C.
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p. 3715 - 3724
(2019/03/30)
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- Copper-Catalyzed Amide Radical-Directed Cyanation of Unactivated Csp3-H Bonds
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A method for site-selective intermolecular δ/?-Csp3-H cyanation of aliphatic sulfonamides is developed using TsCN as the cyanating reagent, catalyzed by a Cu(I)/phenanthroline complex. The mild, expeditious, and modular protocol allows efficient remote Csp3-H cyanation with good functional group tolerance and high regioselectivity. Mechanistic studies indicate that the reaction might proceed through a Cu(I)-mediated N-F bond cleavage to generate an amidyl radical, 1,5-HAT, and cyano group transfer of the resulting carbon radical with TsCN.
- Zhang, Hongwei,Zhou, Yulu,Tian, Peiyuan,Jiang, Cuiyu
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supporting information
(2019/03/19)
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- Sulfonamide-Directed Chemo- and Site-Selective Oxidative Halogenation/Amination Using Halogenating Reagents Generated in Situ from Cyclic Diacyl Peroxides
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The combination of cyclic diacyl peroxides with commercially available halide salts as a unique halogenating system is utilized in Hofmann-L?ffler-Freytag-type reaction. This strategy allows for the formation of N-chloroamides, δ-brominated products, and
- Chang, Denghu,Zhao, Rong,Wei, Congyin,Yao, Yuan,Liu, Yang,Shi, Lei
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p. 3305 - 3315
(2018/03/25)
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- Triiodide-Mediated δ-Amination of Secondary C?H Bonds
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The Cδ?H amination of unactivated, secondary C?H bonds to form a broad range of functionalized pyrrolidines has been developed by a triiodide (I3?)-mediated strategy. By in situ 1) oxidation of sodium iodide and 2) sequestration of the transiently generated iodine (I2) as I3?, this approach precludes undesired I2-mediated decomposition which can otherwise limit synthetic utility to only weak C(sp3)?H bonds. The mechanism of this triiodide-mediated cyclization of unbiased, secondary C(sp3)?H bonds, by either thermal or photolytic initiation, is supported by NMR and UV/Vis data, as well as intercepted intermediates.
- Wappes, Ethan A.,Fosu, Stacy C.,Chopko, Trevor C.,Nagib, David A.
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supporting information
p. 9974 - 9978
(2016/08/16)
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- Direct room-temperature lactonisation of alcohols and ethers onto amides: An "amide strategy" for synthesis
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Last-minute deal: A direct lactonisation of ethers and alcohols onto amides that proceeds at room temperature under mild conditions is reported (see scheme). This allows the effective saving of up to two unproductive, sequential deprotection operations in synthetic sequences. Mechanistic studies are described, and a new "amide strategy" that exploits the dual robustness/late-stage selective activation properties of this functional group is outlined. Copyright
- Valerio, Viviana,Petkova, Desislava,Madelaine, Claire,Maulide, Nuno
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supporting information
p. 2606 - 2610
(2013/03/14)
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- Chemoselective alkynylation of N-sulfonylamides versus amides and carbamates-Synthesis of tetrahydropyrazines
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The chemoselective alkynylation of N-sulfonylamides versus amides and carbamates using TMS-EBX as an alkynylating agent leads to the formation of non-symmetrical tetrahydropyrazines from orthogonally protected diamines. The Royal Society of Chemistry 2013
- Aubineau, Thomas,Cossy, Janine
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supporting information
p. 3303 - 3305
(2013/06/04)
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- TiCl4-mediated direct N-alkylation of sulfonamides with inactive ethers
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A TiCl4-mediated intermolecular or intramolecular direct N-alkylation reaction of sulfonamides with inactive ethers as alkylating agents was successfully achieved. This method provides a novel approach towards N-alkyl sulfonamides from inactive ethers via an easy workup procedure. Georg Thieme Verlag Stuttgart · New York.
- Chen, Jiayan,Dang, Ling,Li, Qiang,Ye, Yong,Fu, Shaomin,Zeng, Wei
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supporting information; experimental part
p. 595 - 600
(2012/03/27)
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- A novel method for the synthesis of vicinal disulfonamides promoted by metallic samarium in aqueous media
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A new method to synthesize vicinal disulfonamides by reductive coupling of N-sulfonylimines in Sm/HCl/THF has been developed and various reaction conditions have been studied.
- Liu, Xi,Liu, Yunkui,Zhang, Yongmin
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p. 6787 - 6789
(2007/10/03)
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