Chemoselective oxidative generation of ortho -quinone methides and tandem transformations

Published on Mar 23, 2020in Nature Chemistry24.427
· DOI :10.1038/S41557-020-0433-4
Muhammet Uyanik23
Estimated H-index: 23
(Nagoya University),
Kohei Nishioka2
Estimated H-index: 2
(Nagoya University)
+ 1 AuthorsKazuaki Ishihara82
Estimated H-index: 82
(Nagoya University)
Sources
Abstract
ortho-Quinone methides are useful transient synthetic intermediates in organic synthesis. These species are most often generated in situ by the acid- or base-mediated transformation of phenols that have been pre-functionalized at a benzylic position, or by biomimetic oxidation of the corresponding ortho-alkylphenols with metal oxidants or transition-metal complexes. Here we describe a method for the transition-metal-free oxidative generation of o-QMs from ortho-alkylarenols, using hypoiodite catalysis under nearly neutral conditions, which can then be applied in one-pot tandem reactions. This method for the chemoselective oxidative generation of ortho-quinone methides may prove superior to previous methods with respect to environmental issues and scope, and can be applied to various tandem reactions such as inter- or intramolecular [4 + 2] cycloaddition, oxa-6π-electrocyclization, conjugate addition and spiroepoxidation. ortho-Quinone methides are highly reactive transient intermediates found in some organic syntheses and biological processes. The generation of these species often requires pre-functionalized substrates and/or metal oxidants, but now the chemoselective oxidative generation of ortho-quinone methides from ortho-alkylarenols has been achieved using hypoiodite catalysis under nearly neutral conditions.
📖 Papers frequently viewed together
References51
Newest
#1Takuya Oguma (Kyushu University)H-Index: 7
#2Daiki Doiuchi (Kyushu University)H-Index: 2
Last. Tsutomu Katsuki (International Institute of Minnesota)H-Index: 86
view all 7 authors...
Source
#1Peishan Kc Chen (UCSB: University of California, Santa Barbara)H-Index: 1
#2Yuk Fai Wong (UCSB: University of California, Santa Barbara)H-Index: 1
Last. Thomas R. R. Pettus (UCSB: University of California, Santa Barbara)H-Index: 31
view all 4 authors...
A one-pot method for joining three separate components leading to an assortment of N-substituted 3,4-dihydro-2H-1,3-benzoxazines is described. The method involves the addition of a Grignard reagent to an o-OBoc salicylaldehyde in the presence of an imine. With a variety of components, 15 examples are presented, including the diastereoselective incorporation of chiral imines.
Source
#1Michael F. McLaughlin (UNC: University of North Carolina at Chapel Hill)H-Index: 3
#2Elisabetta Massolo (UNC: University of North Carolina at Chapel Hill)H-Index: 3
Last. Jeffrey S. Johnson (UNC: University of North Carolina at Chapel Hill)H-Index: 58
view all 4 authors...
Phenols are attractive starting materials for the preparation of highly substituted cyclohexane rings via dearomative processes. Herein we report an efficient preparation of dearomatized 1-oxaspiro[2.5]octa-4,7-dien-6-ones (para-spiroepoxydienones) via the nucleophilic epoxidation of in situ generated para-quinone methides from 4-(hydroxymethyl)phenols using aqueous H2O2. The developed protocol bypasses the need for stoichiometric bismuth reagents or diazomethane, which are frequently deployed f...
Source
#1Michael F. McLaughlin (UNC: University of North Carolina at Chapel Hill)H-Index: 3
#2Elisabetta Massolo (UNC: University of North Carolina at Chapel Hill)H-Index: 3
Last. Jeffrey S. Johnson (UNC: University of North Carolina at Chapel Hill)H-Index: 58
view all 4 authors...
Feedstock aromatic compounds are compelling low-cost starting points from which molecular complexity can be generated rapidly via oxidative dearomatization. Oxidative dearomatizations commonly rely heavily on hypervalent iodine or heavy metals to provide the requisite thermodynamic driving force for overcoming aromatic stabilization energy. This article describes oxidative dearomatizations of 2-(hydroxymethyl)phenols via their derived bis(dichloroacetates) using hydrogen peroxide as a mild oxida...
Source
#1Muhammet Uyanik (Nagoya University)H-Index: 23
#2Kohei Nishioka (Nagoya University)H-Index: 2
Last. Kazuaki Ishihara (Nagoya University)H-Index: 82
view all 3 authors...
The first transition metal-free catalytic oxidative dearomatizative azidation of arenols has been developed using hypoiodite catalysis with aqueous hydrogen peroxide and trimethylsilyl azide as an ...
Source
#1Muhammet Uyanik (Nagoya University)H-Index: 23
#2Naoto Sahara (Nagoya University)H-Index: 4
Last. Kazuaki Ishihara (Nagoya University)H-Index: 82
view all 3 authors...
Source
#1Baochao Yang (ECNU: East China Normal University)H-Index: 1
#2Shuanhu Gao (ECNU: East China Normal University)H-Index: 1
In recent decades, transient and highly reactive ortho-quinodimethanes (o-QDMs), ortho-quinone methides (o-QMs) and aza-ortho-quinone methides (aza-o-QMs) have attracted much attention and have been extensively studied and applied in organic synthesis, especially natural product total synthesis. This review summarizes recent advances in Diels–Alder reactions involving in situ-generated o-QDMs, o-QMs and aza-o-QMs, highlighting the power and potential of this strategy in organic synthesis and nat...
Source
#1Rongxiang Chen (Soochow University (Suzhou))H-Index: 1
#2Jijun Chen (Soochow University (Suzhou))H-Index: 9
Last. Xiaobing Wan (Soochow University (Suzhou))H-Index: 26
view all 4 authors...
In this account, we describe our recent progress on transition-metal-free-catalyzed cross-coupling reactions using tetrabutylammonium iodide (TBAI) as the catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant. A rich variety of important organic compounds including α-acyloxy ethers, tert-butyl peresters, allylic esters, amides, α-amino nitriles, fully substituted pyrazoles, N-sulfonyl formamidines, α-amino acid esters, cyanomethyl esters, N-nitrosamines, and 3-acyloxy-2,3-dihydrobenzofuran...
Source
#1Masayuki Kirihara (Shizuoka Institute of Science and Technology)H-Index: 18
#2Tomohide OkadaH-Index: 6
Last. Yoshikazu KimuraH-Index: 10
view all 6 authors...
The novel oxidant of sodium hypochlorite pentahydrate (NaOCl·5H2O) crystals is now available for industrial and laboratory use. It is superior to conventional aqueous sodium hypochlorite solutions (aq. NaOCl). The crystalline material is 44% NaOCl and contains minimal amounts of sodium hydroxide and sodium chloride, and the aqueous solution, which is prepared from NaOCl·5H2O and water, has a pH of 11–12. Examples of the selective organic synthesis using NaOCl·5H2O involve the oxidations of prima...
Source
#1Konrad Gebauer (Leipzig University)H-Index: 2
#2Franziska Reuß (Leipzig University)H-Index: 1
Last. Christoph Schneider (Leipzig University)H-Index: 46
view all 4 authors...
The combination of an in situ formed MnL3 complex (HL = Hacac or R(C═O)CH2CO2R) and a chiral phosphoric acid HX* allows for a fully catalytic, asymmetric synthesis of 4H-chromenes starting from 2-alkyl-substituted phenols. The aerobic oxidation toward a transient ortho-quinone methide was efficiently catalyzed by a manganese(III) species MnL3 while the ensuing Michael addition of β-dicarbonyl compounds proved to be catalyzed by a chiral manganese phosphate MnL2X*.
Source
Cited By23
Newest
#1Muhammet Uyanik (Nagoya University)H-Index: 23
#2Dai Nagata (Nagoya University)
Last. Kazuaki Ishihara (Nagoya University)H-Index: 82
view all 3 authors...
We report the hypoiodite-catalyzed oxidative C-C homocoupling of arenols to biarenols or biquinones using aqueous hydrogen peroxide as an oxidant. In addition, by combining hypoiodite catalysis and lipophilic Lewis acid-assisted Bronsted acid catalysis under aqueous conditions, we achieved a tandem oxidation/cross-coupling reaction of hydroquinones with electron-rich arenes. These results highlight the substantial scope of hypoiodite/acid co-catalysis for use in oxidative coupling reactions.
Source
#2Ziqi YeH-Index: 3
Last. Lei Gong
view all 8 authors...
Regiodivergent asymmetric cycloadditions from the same set of starting materials offer interesting opportunities for rapid construction of optically active cyclic molecules with structural diversit...
Source
The stunning advances in understanding the reactivity and selectivity principles of asymmetric pericyclic reactions have had a profound impact on the synthetic planning of complex natural products. Indeed, electrocyclizations, cycloadditions, and sigmatropic rearrangements enable synthetic chemists to craft highly functionalized scaffolds that would not otherwise be possible with a similar atom-, step-, and redox-economy. In this review, selected examples from the last two decades of research (2...
Source
#1Zhong ShaoH-Index: 1
#2Fang WangH-Index: 3
Last. Ziyuan Li (Sichuan University)H-Index: 13
view all 5 authors...
Source
#1Priyadarshini Thoppe Sivakumar (National Institute for Interdisciplinary Science and Technology)
#2Sharathna Puthiyaparambath (National Institute for Interdisciplinary Science and Technology)
Last. Radhakrishnan Kokkuvayil Vasu (National Institute for Interdisciplinary Science and Technology)H-Index: 4
view all 5 authors...
Source
#1Xinwei He (Anhui Normal University)H-Index: 14
#2Ruxue Li (Anhui Normal University)H-Index: 6
Last. Fuk Yee Kwong (CUHK: The Chinese University of Hong Kong)H-Index: 64
view all 8 authors...
Existing synthetic routes for accessing dibenzofuran core have intrinsic regioselectivity, limiting the substitution patterns available in heteropolycyclic arene products. Here we report a double 1,4-conjugate addition/intramolecular annulation cascade reaction between propargylamines and two equivalents of imidazolium methylides that allows efficient access of structurally versatile dibenzofurans. This transition metal-free protocol proceeds smoothly under bench-top air atmosphere and offers ea...
Source
#1Keng-Jia Hsu (NTU: National Taiwan University)H-Index: 1
#2Chang-Lin Hsieh (NTU: National Taiwan University)H-Index: 2
Last. Kien Voon Kong (NTU: National Taiwan University)H-Index: 17
view all 4 authors...
Quinone methides (QMs) are very important intermediates in chemistry. These species are most often generated in situ with metal oxidants and transition metal complexes. Here, tip-enhanced Raman spectroscopy (TERS) has been implemented to investigate the in situ oxidative generation of a QM species from alkylphenols facilitated by a transition metal complex. Using TERS, the metal oxidant-mediated transformation of a phenol species has been observed. The subsequent oxidative addition reaction of Q...
Source
#1Abhilash Sharma (AcSIR: Academy of Scientific and Innovative Research)H-Index: 5
#2Hemanta Hazarika (AcSIR: Academy of Scientific and Innovative Research)H-Index: 4
Last. Pranjal Gogoi (AcSIR: Academy of Scientific and Innovative Research)H-Index: 18
view all 3 authors...
In recent decades, o-quinone methides and o-quinone sulfides have been extensively highlighted as reactive intermediates for the synthesis of diversely functionalized ortho-disubstituted arenes and heterocycles. Additionally, ortho-disubstituted arenes offer a constructive path for the synthesis of fused carbocycles, heterocycles, natural products, and drug candidates. In the lieu of that, this Synopsis highlights a comprehensive overview on the potential applications of in situ generated o-quin...
Source
#1Seung Tae Kim (SKKU: Sungkyunkwan University)H-Index: 11
#2Rameshwar Prasad Pandit (SKKU: Sungkyunkwan University)H-Index: 9
Last. Do Hyun Ryu (SKKU: Sungkyunkwan University)H-Index: 40
view all 4 authors...
A Michael addition initiated cyclopropanation/[1,5]-hydrogen shift has been developed for the enantioselective synthesis of Rauhut-Currier products. The reaction of α-alkyl diazoesters and in situ generated o-quinone methides proceeds in the presence of chiral oxazaborolidinium ion, providing Z-stereocontrolled Rauhut-Currier products in high yields (up to 96%) with excellent Z/E selectivities (>20:1) and enantioselectivities (up to >99% ee). The synthetic utility was illustrated by conversion o...
Source
This website uses cookies.
We use cookies to improve your online experience. By continuing to use our website we assume you agree to the placement of these cookies.
To learn more, you can find in our Privacy Policy.