Enantioselective synthesis of epoxides by α-deprotonation—electrophile trapping of achiral epoxides

Hodgson, David M.; Buxton, Timothy; Cameron, Iain; Gras, Emmanuel; Kirton, Eirene H. M.

doi:10.1039/b309717j

Cited by 28 publications

(10 citation statements)

References 38 publications

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“…In the case of highly symmetric bispidones, such as compounds 49-56 (Table II), as well as the comparable 1,5-dialkyl-or 1,5-unsubstituted derivatives, the Wolff-Kishner reaction with hydrazine hydrate (32,88,(108)(109)(110)(111)(112) hydrazide (113,114) leads to the corresponding bispidines, while reduction of these compounds with LiAlH 4 (58,88) or NaBH 4 (115) yields bispidoles (Scheme 8).…”

Section: Reduction Of Bispidonesmentioning

confidence: 99%

Bispidine Coordination Chemistry

Comba

Kerscher

Schiek

2007

Progress in Inorganic Chemistry

142

198

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Section: Reduction Of Bispidonesmentioning

confidence: 99%

Bispidine Coordination Chemistry

Comba

Kerscher

Schiek

2007

Progress in Inorganic Chemistry

142

198

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“…Sulfoxides are useful building blocks as chiral auxiliaries in organic synthesis and possess a wide range of biological activities, such as antimicrobial properties, the inhibition of the biosynthesis of uric acid and the secretion of gastric acid or the regulation of cholesterol catabolism . Epoxides are well‐known as interesting and versatile intermediates or precursors for the synthesis of pharmaceuticals, agrochemicals and many other compounds . The treatment of alkenes with a peroxide‐containing reagent that donates a single oxygen atom in the presence of a transition‐metal catalyst is a famous method for the generation of epoxides under mild conditions.…”

Section: Introductionmentioning

confidence: 99%

Electronic Effects of Aromatic Rings on the Catalytic Activity of Dioxidomolybdenum(VI)–Hydrazone Complexes

et al. 2017

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A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription. This manuscript has been accepted after peer review and appears as an Accepted Article online prior to editing, proofing, and formal publication of the final Version of Record (VoR). This work is currently citable by using the Digital Object Identifier (DOI) given below. The VoR will be published online in Early View as soon as possible and may be different to this Accepted Article as a result of editing. Readers should obtain the VoR from the journal website shown below when it is published to ensure accuracy of information. The authors are responsible for the content of this Accepted Article. FULL PAPER Electronic effects of aromatic rings on the catalytic activity of dioxidomolybdenum(VI)-hydrazone complexesRahman Bikas, [a,*] Vito Lippolis, [b,*] Nader Noshiranzadeh, [a] Hossein Farzaneh-Bonab, [a] Alexander J. Blake, [c] Milosz Siczek, [d] Hassan Hosseini-Monfared, [a] and Tadeusz Lis [d] Abstract:Nine dioxidomolybdenum(VI) complexes were synthesized by the reaction of MoO3 with tridentate hydrazone Schiff base ligands obtained from the reaction of aromatic acid hydrazides (3-hydroxy-2-naphthoic acid hydrazide, 4-pyridine carboxylic acid hydrazide or 2-furane carboxylic acid hydrazide) and ortho-hydroxy aldehyde derivatives (5-iodo-2-hydroxybenzaldehyde, 2-hydroxy-1-naphthaldehyde or 2-hydroxy-3-methoxybenzaldehyde). All ligands and complexes were characterized by elemental analysis and spectroscopic methods. The structures of seven complexes were further elucidated by single-crystal X-ray diffraction analysis which indicated a distorted octahedral geometry at the metal centre. Spectroscopic and X-ray analyses indicated that the ligands are coordinated to the molybdenum(VI) ion as dinegative ligands due to deprotonation of phenolic OH and amidic NH groups upon complexation. These complexes were used as catalyst in the oxidation of cyclooctene and thioanisole in the presence of hydrogen peroxide as environmental friendly oxidant. In order to achieve the highest catalytic activity, the effects of important parameters such as solvent, temperature and the molar ratio of oxidant to substrate were optimized. The results indicate that electron-withdrawing substituents on the ligands increase the catalytic activity of dioxidomolybdenum(VI)-hydrazone complexes.

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“…11a,13a,b,14 The intermolecular trapping of nonstabilized a-lithio ethers was as yet only realized with epoxides. 15,16 Well studied is the enantioselective deprotonation of cyclooctene oxide (5, Scheme 1) with s-BuLi at -90°C in the presence of the chiral auxiliary (-)-sparteine (1). 15 Quench of the resulting anion with electrophiles delivered the a-substituted derivatives 6 in good yields and enantioselectivities.…”

Section: Figurementioning

confidence: 99%

Thieme Chemistry Journal Awardees - Where Are They Now? Bridgehead Lithiated 9-Oxabispidines

Breuning¹,

Steiner²,

Hein³

et al. 2009

Synlett

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Enantioselective synthesis of epoxides by α-deprotonation—electrophile trapping of achiral epoxides

Abstract: Enantioselective alpha-deprotonation of achiral epoxides 1, 21, and 26 using organolithiums in the presence of (-)-sparteine 2 and subsequent electrophile trapping gives access to enantioenriched trisubstituted epoxides 9-17, 22, 23, 27 and 28 (in up to 86% ee).

Cited by 28 publications

References 38 publications

Bispidine Coordination Chemistry

Bispidine Coordination Chemistry

Electronic Effects of Aromatic Rings on the Catalytic Activity of Dioxidomolybdenum(VI)–Hydrazone Complexes

Thieme Chemistry Journal Awardees - Where Are They Now? Bridgehead Lithiated 9-Oxabispidines

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