ChemInform Abstract: A Novel One-Pot Sulfonyloxylactonization of Alkenoic Acids Mediated by Hypervalent Iodine Species Generated in situ from Ammonium Iodide.

ChemInform ◽  
2014 ◽  
Vol 45 (20) ◽  
pp. no-no
Author(s):  
Jiantao Hu ◽  
Min Zhu ◽  
Yuan Xu ◽  
Jie Yan
Author(s):  
Romana Pajkert ◽  
Henryk Koroniak ◽  
Pawel Kafarski ◽  
Gerd Volker Roeschenthaler

A one-pot, regioselective 1,3-dipolar cycloaddition of in situ generated (diethoxyphosphoryl)difluoromethyl nitrile oxide toward selected alkenes and alkynes is reported. This protocol enables facile access to 3,5-disubstituted isoxazolines and isoxazoles bearing...


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Xuemin Li ◽  
Guangchen Li ◽  
Yifu Cheng ◽  
Yunfei Du

Abstract The application of hypervalent iodine species generated in situ in organic transformations has emerged as a useful and powerful tool in organic synthesis, allowing for the construction of a series of bond formats via oxidative coupling. Among these transformations, the catalytic aryl iodide can be oxidized to hypervalent iodine species, which then undergoes oxidative reaction with the substrates and the aryl iodine regenerated again once the first cyclic cycle of the reaction is completed. This review aims to systematically summarize and discuss the main progress in the application of in situ-generated hypervalent iodine species, providing references and highlights for synthetic chemists who might be interested in this field of hypervalent iodine chemistry.


Synthesis ◽  
2020 ◽  
Vol 52 (16) ◽  
pp. 2299-2310 ◽  
Author(s):  
Akira Yoshimura ◽  
Akio Saito ◽  
Viktor V. Zhdankin ◽  
Mekhman S. Yusubov

Organohypervalent iodine reagents are widely used for the preparation of various oxazolines, oxazoles, isoxazolines, and isoxazoles. In the formation of these heterocyclic compounds, hypervalent iodine species can serve as the activating reagents for various substrates, as well as the heteroatom donor reagents. In recent research, both chemical and electrochemical approaches toward generation of hypervalent iodine species have been utilized. The in situ generated active species can react with appropriate substrates to give the corresponding heterocyclic products. In this short review, we summarize the hypervalent-iodine­-mediated preparation of oxazolines, oxazoles, isoxazolines, and isoxazoles starting from various substrates.1 Introduction2 Synthesis of Oxazolines3 Synthesis of Oxazoles4 Synthesis of Isoxazolines5 Synthesis of Isoxazoles6 Conclusion


2019 ◽  
Vol 15 ◽  
pp. 602-609
Author(s):  
Kelsey B LaMartina ◽  
Haley K Kuck ◽  
Linda S Oglesbee ◽  
Asma Al-Odaini ◽  
Nicholas C Boaz

A method for the selective monooxdiation of secondary benzylic C–H bonds is described using an N-oxyl catalyst and a hypervalent iodine species as a terminal oxidant. Combinations of ammonium iodate and catalytic N-hydroxyphthalimide (NHPI) were shown to be effective in the selective oxidation of n-butylbenzene directly to 1-phenylbutyl acetate in high yield (86%). This method shows moderate substrate tolerance in the oxygenation of substrates containing secondary benzylic C–H bonds, yielding the corresponding benzylic acetates in good to moderate yield. Tertiary benzylic C–H bonds were shown to be unreactive under similar conditions, despite the weaker C–H bond. A preliminary mechanistic analysis suggests that this NHPI-iodate system is functioning by a radical-based mechanism where iodine generated in situ captures formed benzylic radicals. The benzylic iodide intermediate then solvolyzes to yield the product ester.


2010 ◽  
Vol 12 (20) ◽  
pp. 4644-4647 ◽  
Author(s):  
Aleksandra A. Zagulyaeva ◽  
Christopher T. Banek ◽  
Mekhman S. Yusubov ◽  
Viktor V. Zhdankin

2011 ◽  
Vol 9 (20) ◽  
pp. 6899 ◽  
Author(s):  
Toshifumi Dohi ◽  
Tomofumi Nakae ◽  
Yohei Ishikado ◽  
Daishi Kato ◽  
Yasuyuki Kita

2011 ◽  
Vol 64 (5) ◽  
pp. 529 ◽  
Author(s):  
Toshifumi Dohi ◽  
Nobutaka Yamaoka ◽  
Itsuki Itani ◽  
Yasuyuki Kita

The rate-accelerating effects of fluoroalcohol solvents for generating trivalent hypervalent iodine species and the conversion into diaryliodonium(iii) salts have been used for the first time to realize a facile and clean one-pot synthesis of diaryliodonium(iii) salts 3 from aryl iodides 1 and suitable arene partners 2 with peracetic acid (PAA). The use of PAA as a green and practical oxidant is significantly effective in fluoroalcohol solvents. The scope and limitations of the methodology are elucidated by investigation of a wide variety of representative substrates.


ChemInform ◽  
2012 ◽  
Vol 43 (12) ◽  
pp. no-no
Author(s):  
Toshifumi Dohi ◽  
Tomofumi Nakae ◽  
Yohei Ishikado ◽  
Daishi Kato ◽  
Yasuyuki Kita

Synthesis ◽  
2021 ◽  
Author(s):  
Victor Martín-Heras ◽  
Constantin G. Daniliuc ◽  
Ryan Gilmour

The heptafluoroisopropyl group is emerging as a privileged chemotype in contemporary agrochemistry and features prominently in the current portfolio of leading insecticides. To reconcile the expansive potential of this module with the synthetic challenges associated with preparing crowded, fluorinated motifs, I(I)/I(III) catalysis has been leveraged. Predicated on in situ generation of p-TolIF2, this route enables the direct difluorination of α-trifluoromethyl-β-difluoro-styrenes in a single operation. This formal addition of fluorine across the alkene π-bond is efficient (up to 91%) and is compatible with a broad range of functional groups. The ArCF(CF3)2 moiety is conformationally pre-organized, with the C(sp3)-F bond co-planar to the framework of the aryl ring, thereby minimizing 1,3-allylic strain. Moreover, orthogonal multipolar C-F•••C=O interactions have been identified in a phathalimide derivative. It is envisaged that this programmed vicinal difluorination enabled by a hypervalent iodine species will find application in functional molecule design in a broader sense.


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