Direct oxidative cyanation of tertiary amines promoted by in situ generated hypervalent iodine(III)-CN intermediate

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...

Download Full-text

Hypervalent Iodine-Mediated Oxygenation of N,N-Diaryl Tertiary Amines: Intramolecular Functionalization of sp3 C–H Bonds Adjacent to Nitrogen

The Journal of Organic Chemistry ◽

10.1021/jo5016823 ◽

2014 ◽

Vol 79 (21) ◽

pp. 10581-10587 ◽

Cited By ~ 54

Author(s):

Ningning Zhang ◽

Ran Cheng ◽

Daisy Zhang-Negrerie ◽

Yunfei Du ◽

Kang Zhao

Keyword(s):

Hypervalent Iodine ◽

Tertiary Amines

Download Full-text

Hypervalent iodine catalysis for selective oxidation of Baylis–Hillman adducts via in situ generation of o-iodoxybenzoic acid (IBX) from 2-iodosobenzoic acid (IBA) in the presence of oxone

New Journal of Chemistry ◽

10.1039/c6nj02628a ◽

2016 ◽

Vol 40 (12) ◽

pp. 10300-10304 ◽

Cited By ~ 10

Author(s):

Raktani Bikshapathi ◽

Parvathaneni Sai Prathima ◽

Vaidya Jayathirtha Rao

Keyword(s):

Selective Oxidation ◽

Carbonyl Compounds ◽

Hypervalent Iodine ◽

In Situ Generation ◽

Iodosobenzoic Acid ◽

High Yields

An efficient, eco-friendly protocol for selective oxidation of primary and secondary Baylis–Hillman alcohols to the corresponding carbonyl compounds in high yields has been developed with 2-iodosobenzoic acid (IBA).

Download Full-text

The aryl iodine-catalyzed organic transformation via hypervalent iodine species generated in situ

Physical Sciences Reviews ◽

10.1515/psr-2021-0019 ◽

2021 ◽

Vol 0 (0) ◽

Author(s):

Xuemin Li ◽

Guangchen Li ◽

Yifu Cheng ◽

Yunfei Du

Keyword(s):

Organic Synthesis ◽

Oxidative Coupling ◽

Hypervalent Iodine ◽

Organic Transformations ◽

Aryl Iodide ◽

Oxidative Reaction ◽

Iodine Species ◽

Iodine Chemistry

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.

Download Full-text

Hypervalent Iodine(III)-Catalyzed Epoxidation of β-Cyanostyrenes

Synthesis ◽

10.1055/s-0039-1690621 ◽

2019 ◽

Vol 51 (23) ◽

pp. 4473-4486 ◽

Cited By ~ 1

Author(s):

Saeesh R. Mangaonkar ◽

Fateh V. Singh

Keyword(s):

Reaction Time ◽

Room Temperature ◽

Hypervalent Iodine ◽

Short Reaction Time ◽

Convenient Approach

A convenient approach for the synthesis of β-cyanoepoxides is illustrated by iodine(III)-catalyzed epoxidation of electron-deficient β-cyanostyrenes, wherein the active catalytic iodine(III) species was generated in situ. The epoxidation of β-cyanostyrenes was performed using 10 mol% PhI as precatalyst in the presence of 2.0 equivalents Oxone as an oxidant and 2.4 equivalents of TFA as an additive at room temperature under ultrasonic radiations. The β-cyanoepoxides were isolated in good to excellent yields in a short reaction time.

Download Full-text

Synthesis of Oxazoline and Oxazole Derivatives by Hypervalent-Iodine-Mediated Oxidative Cycloaddition Reactions

Synthesis ◽

10.1055/s-0040-1707122 ◽

2020 ◽

Vol 52 (16) ◽

pp. 2299-2310 ◽

Cited By ~ 4

Author(s):

Akira Yoshimura ◽

Akio Saito ◽

Viktor V. Zhdankin ◽

Mekhman S. Yusubov

Keyword(s):

Heterocyclic Compounds ◽

Short Review ◽

Active Species ◽

Hypervalent Iodine ◽

Cycloaddition Reactions ◽

Iodine Species ◽

Oxazole Derivatives

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

Download Full-text

Selective benzylic C–H monooxygenation mediated by iodine oxides

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.15.55 ◽

2019 ◽

Vol 15 ◽

pp. 602-609

Author(s):

Kelsey B LaMartina ◽

Haley K Kuck ◽

Linda S Oglesbee ◽

Asma Al-Odaini ◽

Nicholas C Boaz

Keyword(s):

Selective Oxidation ◽

High Yield ◽

Hypervalent Iodine ◽

Iodine Species ◽

Mechanistic Analysis ◽

Substrate Tolerance ◽

Iodine Oxides ◽

Moderate Yield

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.

Download Full-text