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Review
. 2015 Dec 1;54(49):14638-58.
doi: 10.1002/anie.201505017. Epub 2015 Nov 4.

Quinone-Catalyzed Selective Oxidation of Organic Molecules

Alison E Wendlandt  1 , Shannon S Stahl  2
Affiliations
Review

Quinone-Catalyzed Selective Oxidation of Organic Molecules

Alison E Wendlandt et al. Angew Chem Int Ed Engl. .

Abstract

Quinones are common stoichiometric reagents in organic chemistry. Para-quinones with high reduction potentials, such as DDQ and chloranil, are widely used and typically promote hydride abstraction. In recent years, many catalytic applications of these methods have been achieved by using transition metals, electrochemistry, or O2 to regenerate the oxidized quinone in situ. Complementary studies have led to the development of a different class of quinones that resemble the ortho-quinone cofactors in copper amine oxidases and mediate the efficient and selective aerobic and/or electrochemical dehydrogenation of amines. The latter reactions typically proceed by electrophilic transamination and/or addition-elimination reaction mechanisms, rather than hydride abstraction pathways. The collective observations show that the quinone structure has a significant influence on the reaction mechanism and has important implications for the development of new quinone reagents and quinone-catalyzed transformations.

Keywords: amine oxidase; chloranil; dehydrogenation; oxidation; quinones.

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Figures

Scheme 1
Scheme 1
The anthraquinone oxidation (AO) process for industrial synthesis of H2O2, consisting of the sequential autoxidation and hydrogenation of a quinone mediator.
Scheme 2
Scheme 2
Use of quinones as redox shuttles in organic synthesis, represented here in Pd-catalyzed aerobic diacetoxylation of cyclohexadiene, involving Pd, quinone, and metal-macrocycle (LM)-coupled catalytic cycles.[6]
Scheme 3
Scheme 3
Hydride-transfer-initiated reaction pathways that accounts for the majority of known DDQ-mediated oxidation/dehydrogenation reactions.
Scheme 4
Scheme 4
An electrophilic/polar pathway proposed for DDQ-mediated dehydrogenation of ketones and silyl enol ethers, together with an unproductive, competing electron-transfer (ET) pathway leading to a C–O coupled adduct. Scheme adapted from ref .
Scheme 5
Scheme 5
A generic representation of quinone-catalyzed substrate oxidation employing stoichiometric transition metal as the terminal oxidant.
Scheme 6
Scheme 6
Catalytic oxidation of activated alcohols using catalytic DDQ with periodic acid under biphasic conditions.[40]
Scheme 7
Scheme 7
(A) Oxidation of activated alcohols using catalytic DDQ with Mn(OAc)3 as the terminal oxidant. (B) Selective oxidation of allylic alcohols over benzylic alcohols.[41]
Scheme 8
Scheme 8
Catalytic deprotection of PMB ethers using DDQ in combination with (A) 3.0 equiv FeCl3, or (B) 3.0 equiv Mn(OAc)3 as the (super)stoichiometric terminal oxidant.[42]
Scheme 9
Scheme 9
(A) Stoichometric DDQ-mediated oxidative intramolecular synthesis of tetrahydropyranone derivatives,[28k] and (B) subsequently-developed catalytic conditions for similar transformations.[44]
Scheme 10
Scheme 10
Examples of DDQ-catalyzed transformations with MnO2 as the terminal oxidant: (A) PMB deprotection, (B) arene and (C) heteroarene dehydrogenation reactions, as well as (D) CDC reaction of isochroman with acetophenone, based on reaction conditions developed for tetrahydropyranone synthesis.[44]
Scheme 11
Scheme 11
(A) Stoichiometric DDQ-mediated oxidative cyclization reaction towards the synthesis of Zampanolide,[45] and (B) subsequently developed DDQ-catalyzed conditions employing 2.0 equiv CAN as terminal oxidant.[46]
Scheme 12
Scheme 12
DDQ-catalyzed oxidative C-O coupling of diarylmethane C–H bonds employing MnO2 as the terminal oxidant.[47]
Scheme 13
Scheme 13
Cross-dehydrogenative coupling of activated C–H bonds with aryl Grignard reagents using (A) stoichiometric DDQ,[48] or (B) catalytic DDQ with [bis(trifluoroacetoxy)iodo]-benzene (PIFA) as stoichiometric oxidant.[49]
Scheme 14
Scheme 14
Generic representation of electrochemical quinone-catalyzed oxidation of organic substrates.
Scheme 15
Scheme 15
Stoichiometric DDQ-promoted Diels-Alder reaction of compound 5 leads to desired product with (A) β-pinene, but not with (B) α-phellandrene as the reaction partner.[52] (C) Reaction with α-phellandrene is successful when electrochemical catalytic DDQ conditions are employed.[53]
Scheme 16
Scheme 16
Electrochemical DDQ-catalyzed dehydrogenation of C–N bonds by controlled potential electrolysis at 0.964 V.[16]
Scheme 17
Scheme 17
A generic representation of aerobic quinone-catalyzed substrate oxidation employing (A) an electron transfer mediator (ETM) or (B) NO/NO2 redox couple to facilitate hydroquinone reoxidation.
Scheme 18
Scheme 18
Aerobic oxidation of tetrachlorohydroquinone and other hydroquinone derivatives to corresponding quinones using polymer incarcerated Pt (PI Pt) nanoclusters.[60]
Scheme 19
Scheme 19
Aerobic o-chloranil-catalyzed dehydrogenation of (A) dihydropyridines to pyridines and (B) 2-methylindoline to 2-methylindole using co-catalytic hybrid organic/inorganic platinum nanocluster catalyst (HB Pt), and (C) PMB ether deprotection under similar conditions employing oxidation-resistant polymer-incarcerated Pt co-catalyst (RPI Pt).[61]
Scheme 20
Scheme 20
Stoichiometric oxidation of tetrahydroquinoline derivative 6, with 3.0 eq chloranil leads to substrate/chloranil ketal adduct 8. Desired product 7 can be obtained under previously-developed catalytic conditions.[61]
Scheme 21
Scheme 21
NO2-catalyzed aerobic oxidation of hydroquinones to quinones.[63]
Scheme 22
Scheme 22
DDQ-catalyzed aerobic dehydrogenation of dihydroanthracene employing co-catalytic NaNO2 at elevated temperatures and pressures.[65]
Scheme 23
Scheme 23
DDQ-catalyzed aerobic oxidation of (A) alcohols and (B) ethers, and (C) selective deprotection of PMB using tert-butylnitrite as a co-catalyst.[66]
Scheme 24
Scheme 24
DDQ-catalyzed aerobic oxidation of activated alcohols to aldehydes employing co-catalytic NaNO2 under mild conditions.[67]
Scheme 25
Scheme 25
DDQ-catalyzed aerobic C-C coupling of diarylpropenes and 1,3-dicarbonyls employing co-catalytic NaNO2.[73]
Scheme 26
Scheme 26
Copper amine oxidases carry out (A) the aerobic oxidation of primary amines in vivo. Two initially-proposed substrate oxidation mechanisms, the (B) transamination mechanism, and (C) addition-elimination mechanism. Scheme adapted from ref .
Scheme 27
Scheme 27
Aerobic primary amine oxidation catalyzed by model quinone cofactors (A) TBHBQ, developed by Klinman,[83] (B) Piv-TPQ, developed by Sayre,[84] and (C)Me-TTQ, developed by Itoh.[85]
Scheme 28
Scheme 28
Mechanistic proposal for C-H bond breaking step in biomimetic model quinone- catalyzed aerobic oxidation of primary amines to imines, involving competing intramolecular (“spontaneous”) and intermolecular (“base-catalyzed”) C-H cleavage steps.[85a]
Scheme 29
Scheme 29
Proposed mechanism of alcohol oxidation mediated by cofactor PQQ.
Scheme 30
Scheme 30
Biomimetic, aerobic oxidation of methanol and ethanol catalyzed by PQQ-3OMe.[88]
Scheme 31
Scheme 31
(A) PQQ and model compounds, didecarboxy PQQ and phenanthroline-derived quinones. (B) Adduct formation is observed in the reaction of 4,7-phenanthroline-1,10-dione with excess morpholine, implicating the transamination mechanism.[93] (C) Different reaction mechanisms lead to different reduction products, detected by end-product analysis.
Scheme 32
Scheme 32
Stoichiometric oxidation of branched primary amines to ketones using 3,5-di-tert-butyl-o-quinone. Oxazole adducts are obtained when unbranched primary amines are used as substrates.[101]
Scheme 33
Scheme 33
(A) Aerobic oxidation of aminohydroquinone results in formation of dimeric species 15, (B) and additional approaches to regenerate quinone from reduced aminohydroquinone.[104]
Scheme 34
Scheme 34
Catalytic oxidation of primary amines to aldehydes and ketones using PQQ promoted by micellar conditions.[105]
Scheme 35
Scheme 35
(A) Electrochemical oxidation of amines to imines[107] and (B) secondary amines, [108] by CAO mimics Q1red and Q2red. (C) When CuI is added as a co-catalyst, the aerobic oxidation of primary amines is also achieved.[109]
Scheme 36
Scheme 36
Aerobic oxidation of primary amines to imines using biomimetic o-quinone catalyst TBHBQ.[110]
Scheme 37
Scheme 37
Aerobic oxidation of a-branched primary amines to imines using a biomimetic o-quinone catalyst, Q3. [112]
Scheme 38
Scheme 38
Irreversible pyrrolation of TBHBQ catalyst via transamination-type mechanism is observed when 3-pyrroline substrates are used.[113]
Scheme 39
Scheme 39
(A) Dehydrogenation of C-N bonds using Pt/Ir alloy incarcerated coblock polymer catalyst, (B) used in combination with co-catalytic catechol additives. (C) A mechanism is proposed wherein substrate oxidation by Pt involved quinone-substrate hemiaminal intermediates.[114]
Scheme 40
Scheme 40
(A) Conditions for the aerobic phd-catalyzed oxidation of a variety of secondary amines, (B). (C) An “addition-elimination” mechanism is proposed involving a hemiaminal intermediate.[116]
Scheme 41
Scheme 41
Dehydrogenation of tetrahydroquinolines to quinolines under ambient conditions with co-catalyst system consisting of [Ru(phd)3](PF6)2 and [Co(salophen)].
Scheme 42
Scheme 42
Influence of different Lewis acid promoters and co-catalysts on the quinone-catalyzed aerobic dehydrogenation of tetrahydroquinoline to quinoline by phd and phd-coordinated Ru complexes. Scheme adapted from ref .
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