Asymmetric Permanganate-Promoted Oxidative Cyclization of 1,5-Dienes by Using Chiral Phase-Transfer Catalysis This work was supported by the EPSRC (J.F.K.) and the Royal Society (R.C.D.B.). We thank Dr. Barry Lygo (University of Nottingham) for helpful discussions, and Syngenta and Merck Sharp and Dohme for unrestricted grants.

Brown, Richard C. D.; Keily, John F.

doi:10.1002/1521-3773(20011203)40:23<4496::aid-anie4496>3.0.co;2-f

Cited by 83 publications

(18 citation statements)

References 4 publications

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“…It should be noted that the stereochemistry of the permanganate-mediated cyclization allows the elegant assembly of the tetrahydrofuran-diol portion of some of these products. For example, in the synthesis of cis-solamin, 23 a threo-cis-threo mono-tetrahydrofuran acetogenin, the pivotal cyclization step of diene 11 (Scheme 11, top), derivatized with (2S)-10,2-camphorsultam, was accomplished in a 55% yield and 10:1 diastereomeric ratio under phase-transfer conditions 24 (see below), previously set up by the same authors, with ethyl acetate as solvent. This result also demonstrated that new conditions had to be devised in order to induce unbranched 1,5-dienes to cyclize in reasonable yields.…”

Section: Scheme 7 Permanganate-mediated Diastereoselective Oxidative mentioning

confidence: 99%

“…28 The first, which was cis-stereoselective, was performed with potassium permanganate in acetone-acetic acid; the second, carried out with trifluoroacetyl perrhenate (from Re 2 O 7 -TFAA), allowed for the closure of the trans-tetrahydrofuran ring, with the anticipated stereoselectivity based on that displayed in the hydroxyl-directed oxidative cyclization of bishomoallylic alcohols with rhenium(VII) oxides. 29 Brown and Keily 24 were also able to obtain promising levels of asymmetric induction by performing the oxidative 31 The presence of a catalytic amount of water was crucial to this process, and a large amount of both potassium permanganate (25 equiv) and copper(II) sulfate pentahydrate (11 equiv) was employed. In some cases, minor amounts (8-10%) of the related d-lactones were obtained.…”

Section: Scheme 7 Permanganate-mediated Diastereoselective Oxidative mentioning

confidence: 99%

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Oxidative Cyclization of Dienes and Polyenes Mediated by Transition-Metal-Oxo Species

Piccialli¹

2007

Synthesis

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During the last forty years, several groups have reported results concerning the oxidative cyclization of polyenes, mostly dienes, with transition-metal-oxo species such as permanganate, ruthenium tetroxide, perruthenate and osmium tetroxide, but only recently has a systematic study of some of these processes been undertaken. The formation in a single step of tetrahydrofuran, polytetrahydrofuran, tetrahydropyran and oxepane products with complete relative stereocontrol, and the unique postulated mechanisms, render these processes very appealing from both the synthetic and theoretical points of view. Recent synthetic applications of these oxidative transformations have highlighted their usefulness. This review summarizes the state of the art in this field, in an attempt to provide a comprehensive view of these processes. Some similarities between the chemistry of ruthenium tetroxide and rhenium(VII)-oxo species are highlighted.

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Section: Scheme 7 Permanganate-mediated Diastereoselective Oxidative mentioning

confidence: 99%

Section: Scheme 7 Permanganate-mediated Diastereoselective Oxidative mentioning

confidence: 99%

Oxidative Cyclization of Dienes and Polyenes Mediated by Transition-Metal-Oxo Species

Piccialli¹

2007

Synthesis

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“…Previously established standard conditions using acetone–water delivered THF-diol 28a in only 18% yield. Better results were achieved when the oxidative cyclization was carried out under phase-transfer conditions [84]. Thus, the corresponding THF diols were obtained in 55% yield.…”

Section: Reviewmentioning

confidence: 99%

The direct oxidative diene cyclization and related reactions in natural product synthesis

Adrian¹,

Gross²,

Stark³

2016

Beilstein J. Org. Chem.

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SummaryThe direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (dia)stereoselective preparation of substituted tetrahydrofurans. Closely related reactions start from 5,6-dihydroxy or 5-hydroxyalkenes to generate similar products in a mechanistically analogous manner. After a brief overview on the history of this group of transformations and a survey on mechanistic and stereochemical aspects, this review article provides a summary on applications in natural product synthesis. Moreover, current limitations and future directions in this area of chemistry are discussed.

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“…The addition of acetic acid is quite important for the reaction to proceed, and highly functionalized tetrahydrofurans are obtained in a range of 58 to 75% ee, in diastereoselective manner [35]. Another oxidative transformation using KMnO 4 with a chiral ammonium salt has been investigated.…”

Section: Asymmetric Oxygen-functionalizationmentioning

confidence: 99%

Cinchona‐Derived Chiral Phase‐Transfer Catalysts for Other Asymmetric Synthesis

Arai

2008

Asymmetric Phase Transfer Catalysis

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Phase-transfer catalysis has been recognized as one of the most powerful synthetic tools for establishing practical protocols because it offers several advantages, such as operational simplicity, mild conditions with aqueous media, suitability for large-scale reaction, and an environmentally benign nature. Since the pioneering studies on asymmetric alkylation promoted by chiral phase-transfer catalysts (PTCs) [1,2], this research area has served as an attractive area for the pursuit of green chemistry, and many types of chiral quaternary ammonium salts for various asymmetric phasetransfer catalyses have been developed over the past few decades [3,4]. For example, two-center organocatalysis using bis-ammonium salts derived from tartrate represents a new concept in asymmetric PTC chemistry [5].In particular, it is not only the cinchona alkaloids that are suitable chiral sources for asymmetric organocatalysis [6], but also the corresponding ammonium salts. Indeed, the latter are particularly useful for chiral PTCs because: (1) both pseudo enantiomers of the starting amines are inexpensive and available commercially; (2) various quaternary ammonium salts can be easily prepared by the use of alkyl halides in a single step; and (3) the olefin and hydroxyl functions are beneficial for further modification of the catalyst. In this chapter, the details of recent progress on asymmetric phase-transfer catalysis are described, with special focus on cinchonaderived ammonium salts, except for asymmetric alkylation in a-amino acid synthesis. Asymmetric Darzens ReactionThe Darzens reaction is a fundamental reaction, the products of which are extremely useful for the synthesis of other molecules. Despite these advantages, the reaction Asymmetric Phase Transfer Catalysis. Edited by Keiji Maruoka

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Abstract: Up to four new stereocenters are created with control of the relative and absolute stereochemistry in a single step in the unusual phase‐transfer‐catalyzed oxidative cyclization of achiral dienes with permanganate (see scheme).

Cited by 83 publications

References 4 publications

Oxidative Cyclization of Dienes and Polyenes Mediated by Transition-Metal-Oxo Species

Oxidative Cyclization of Dienes and Polyenes Mediated by Transition-Metal-Oxo Species

The direct oxidative diene cyclization and related reactions in natural product synthesis

Cinchona‐Derived Chiral Phase‐Transfer Catalysts for Other Asymmetric Synthesis

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