Preparation of TADOOH, a Hydroperoxide from TADDOL, and Use in Highly Enantioface- and Enantiomer-Differentiating Oxidations

Aoki, Masao; Seebàch, Dieter

doi:10.1002/1522-2675(20010131)84:1<187::aid-hlca187>3.0.co;2-o

Cited by 100 publications

(52 citation statements)

References 35 publications

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“…In order to minimize the number of reactants, we next intended to combine the oxidizing agent and the chiral source. Therefore, we applied the synthesized chiral hydroperoxide TADOOH IX, which is generally known for its high efficiency for sulfoxidation reactions [61]. A striking feature of this method is that no further external catalyst is needed.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of (R)-Modafinil via Organocatalyzed and Non-Heme Iron-Catalyzed Sulfoxidation Using H2O2 as an Environmentally Benign Oxidant

2017

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Abstract:The first organocatalyzed sulfoxidation reaction towards enantioenriched (R)-modafinil (Armodafinil ® ), a drug against narcolepsy, is reported here. A series of chiral organocatalysts, e.g., different chiral BINOL-phosphates, or a fructose-derived N-substituted oxazolidinone ketone (Shi catalyst) were applied for the sulfoxidation reaction with environmentally friendly H 2 O 2 as a convenient oxygen transferring agent. Furthermore, the potential of a biomimetic catalytic system consisting of FeCl 3 and a dipeptide-based chiral ligand was demonstrated, which constitutes the most successful asymmetric non-heme iron-catalyzed synthesis of (R)-modafinil so far.

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Section: Resultsmentioning

confidence: 99%

Synthesis of (R)-Modafinil via Organocatalyzed and Non-Heme Iron-Catalyzed Sulfoxidation Using H2O2 as an Environmentally Benign Oxidant

2017

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“…Thanks to the high robustness of POM catalyst, loadings down to 0.002% could be employed and TONs up to 42,000 were achieved without any decrease in enantioselectivity. The protocol has an additional value: TADDOL can be easily recovered without loss of enantiopurity and recycled into the chiral hydroperoxide [46].…”

Section: Fig 14mentioning

confidence: 99%

Recent advances in vanadium catalyzed oxygen transfer reactions

Licini

Conte

Coletti

et al. 2011

Coordination Chemistry Reviews

160

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Vanadium complexes have proven to be effective catalysts for the activation of peroxides and the selective oxidation of substrates like bromides, sulfides and alkenes. Besides their capability to form metalloperoxo species, which effectively transfer oxygen atoms to the substrate, these systems are synthetically useful for obtaining valuable oxidized molecules on a preparative scale, with a high degree of selectivity and TONs. Furthermore, the use of environmentally friendly oxidants like hydrogen and alkyl hydroperoxides increases significantly their potential application at an industrial level. Here we report a critical survey on the most effective homogeneous vanadium catalysts reported in the last decade concerning their synthetic application in oxygen transfer reactions (sulfoxidation, epoxidation, haloperoxidation) using hydrogen peroxide or alkyl hydroperoxides, demonstrating the different classes of ligands and complexes, their catalytic performances, their reactivity, chemo, stereo and substrate selectivity. Some examples of the use of non conventional reaction media or techniques and catalyst recycling studies will be also discussed

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“…52 On the other hand, direct epoxidation of the ketone has been performed with modest enantioselectivity using a chiral hydroperoxide (Scheme 1, b). 38 To the best of our knowledge, this is the first example of a catalytic methodology that can epoxidize this kind of olefins with excellent ee's. Mechanistic studies.…”

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confidence: 92%

Iron Catalyzed Highly Enantioselective Epoxidation of Cyclic Aliphatic Enones with Aqueous H₂O₂

et al. 2016

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An iron complex with a C 1 -symmetric tetradentate N-based ligand catalyze the asymmetric epoxidation of cyclic enones and cyclohexene ketones with aqueous hydrogen peroxide, providing the corresponding epoxides in good to excellent yields and enantioselectivities (up to 99 % yield, and 95 % ee), under mild conditions and in short reaction times. Evidence is provided that reactions involve an electrophilic oxidant, and this element is employed in performing site selective epoxidation of enones containing two alkene sites.Introduction. Asymmetric epoxidation is a valuable reaction because chiral epoxides are versatile building blocks in synthetic organic chemistry. 1-4 Catalytic epoxidation methodologies based on iron complexes and peroxides (especially H 2 O 2 ), which can be considered as biologically inspired, are interesting because of the availability and low environmental impact of these reagents. [5][6][7][8][9][10][11][12][13][14][15]16 Despite appealing, the approach is challenging because it requires the design of iron coordination complexes that can activate the O-O bond of peroxides to create selective metal based oxidants, and avoid the often facile production of hydroxyl radicals via the Fenton reaction. 10,11,17,18 Recent reports have disclosed successful examples where asymmetric epoxidation is accomplished, in some cases producing high levels of stereoselectivity ( Figure 1). [19][20][21][22][23][24][25][26][27] Highly enantioselective epoxidation of difficult substrates such as ,-disubstituted aromatic enones and -alkyl styrenes, not accessible by other methods, have also been described. 23,24 However, a major limitation still resides at the fact that iron catalyzed asymmetric epoxidations have been limited in scope to olefins conjugated to aromatic rings, [19][20][21][22]23,[24][25][26][27][28][29][30][31][32][33][34][35] and remains to be accomplished for aliphatic substrates. Particularly interesting are cyclic aliphatic enones. Cyclic -epoxide enones are structures found in a number of natural products, 36 and are also valuable synthons that can be further elaborated into precious building blocks for organic synthesis. 37 However, their asymmetric epoxidation is notoriously difficult. Modest to good enantioselectivities have been obtained with chiral hydroperoxides, 38,39 poly(aminoacids) catalysts, 40 ammonium salt catalysts, [41][42][43] and metal based catalysts 21,22,44,45 , but excellent enantioselectivities have only been described by List and co-workers using cinchona alkaloid derived organocatalysts and hydrogen peroxide as oxidant. The main drawbacks of this system are the requirement of relatively high catalyst loadings (up to 10 %) and long reaction times (from 24 to 168 h). In addition,  and ' substituted enones are not valid substrates for the system. Highly enantioselective epoxidations that could improve these aspects will

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Preparation of TADOOH, a Hydroperoxide from TADDOL, and Use in Highly Enantioface- and Enantiomer-Differentiating Oxidations

Cited by 100 publications

References 35 publications

Synthesis of (R)-Modafinil via Organocatalyzed and Non-Heme Iron-Catalyzed Sulfoxidation Using H2O2 as an Environmentally Benign Oxidant

Synthesis of (R)-Modafinil via Organocatalyzed and Non-Heme Iron-Catalyzed Sulfoxidation Using H2O2 as an Environmentally Benign Oxidant

Recent advances in vanadium catalyzed oxygen transfer reactions

Iron Catalyzed Highly Enantioselective Epoxidation of Cyclic Aliphatic Enones with Aqueous H₂O₂

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Preparation of TADOOH, a Hydroperoxide from TADDOL, and Use in Highly Enantioface- and Enantiomer-Differentiating Oxidations

Cited by 100 publications

References 35 publications

Synthesis of (R)-Modafinil via Organocatalyzed and Non-Heme Iron-Catalyzed Sulfoxidation Using H2O2 as an Environmentally Benign Oxidant

Synthesis of (R)-Modafinil via Organocatalyzed and Non-Heme Iron-Catalyzed Sulfoxidation Using H2O2 as an Environmentally Benign Oxidant

Recent advances in vanadium catalyzed oxygen transfer reactions

Iron Catalyzed Highly Enantioselective Epoxidation of Cyclic Aliphatic Enones with Aqueous H2O2

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Resources

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Iron Catalyzed Highly Enantioselective Epoxidation of Cyclic Aliphatic Enones with Aqueous H₂O₂