Reaction of 3-phenylglycidic esters. Part 2. Stereo- and regio-selectivity in the oxirane ring opening of methyl trans-3-(4-methoxyphenyl)glycidate with various thiophenols and the effects of solvent and temperature

Hashiyama, Tomiki; Inoue, Hirozumi; Takeda, Mikio; Aoe, Keiichi; Kotera, Keishi

doi:10.1039/p19850000421

Cited by 24 publications

(9 citation statements)

References 4 publications

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“…[33] Competition between both these two mechanisms could also account for the stereoselective outcome of this substitution. In the case of an S N 1-type mechanism, the substitution would proceed through a carbocation or the equivalent p-quinone methide intermediate.…”

Section: Resultsmentioning

confidence: 98%

Oxidative Nucleophilic Substitution (S_NOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

2007

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Synthetic investigations of 1,3‐dichloro‐5,6‐dicyanobenzoquinone‐mediated benzylic oxidation is reported for the synthesis of natural alkaloid analogues. Extensive explorations of the oxidative nucleophilic substitution of the benzylic position of β‐phenylethylamine derivatives and the synthesis of functionalized tetrahydroisoquinolines of ecteinascidin 743 precursors have been carried out. Starting from L‐DOPA, a tunable oxazolidinone group was installed under oxidative benzylic conditions. This derivative 13 was submitted to benzylic oxidation reactions using a wide range of carboxylic acids and subsequent chemical transformations of these compounds were attempted. Moreover, an efficient synthesis of an aromatic ketone derivative 20 was achieved and gave rise to tetrahydroisoquinoline 24 through a direct Pictet–Spengler cyclisation reaction. Subsequently, 24 was transformed into functionalized α‐amino alcohols 31a and 31b, precursors of ecteinascidin 743 analogues. In addition, in order to assess the viability of our synthetic strategy, the reaction of 24 with methyl thioglycolate was performed and the stereoselectivity confirmed by X‐ray analysis of 33a. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: Resultsmentioning

confidence: 98%

Oxidative Nucleophilic Substitution (S_NOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

2007

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“…Inoue and co-workers from Tanabe Seiyaku and Schwartz et al from Hoffmann-La Roche demonstrated that the cis opening of epoxides also takes place predominantly at higher temperatures even in the absence of any catalyst. However, the mechanism for this reaction is still controversial.…”

Section: Asymmetric Epoxidationmentioning

confidence: 99%

Catalytic Approaches to Optically Active 1,5-Benzothiazepines

Asano

Matsubara

2018

ACS Catal.

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The 1,5-benzothiazepine framework is well-known as a versatile pharmacophore, and its derivatives have numerous biological activities. Therefore, various synthetic routes to these important compounds have already been investigated. However, in light of the increase in optically active pharmaceuticals, it is of significance to also develop enantioselective synthetic methods. Among various strategies, methods based on enantioselective catalysis are generally efficient in both academia and industry with respect to different factors such as atom or step economy, economic reasons, and diversity-oriented synthesis. While various methodologies had already been investigated until the 1990s, soon after the discovery of marketed pharmaceuticals such as diltiazem, a blockbuster drug containing a 1,5-benzothiazepine unit, additional catalytic strategies also appeared. Thus, this Perspective provides an account of the progress on enantioselective catalysis for the asymmetric synthesis of 1,5-benzothiazepine derivatives.

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“…3 In fact, ring-opening of 1,2-oxiranes with thiols yields b-hydroxy thioethers, which can be used in the synthesis of leukotrienes, 4 HIV-1 protease inhibitors, 3e and MMP inhibitors. 3d Such ring-openings are promoted either by Lewis acids [Zn(II) halides, 5 LiClO 4 , 2d Ln(III) complexes, 2b Ti(i-PrO) 4 , 2i,6 COCl 2 , 1g BF 3 •OEt 2 , 7 Sn(II) salts, 8 InCl 3 2j ] or by basic catalysts (alumina, 9 quaternary ammonium salts, 2c,e,10 including TBAF, and amines 11 ) and afford bhydroxy sulfides in good yields with high regiochemical control.…”

mentioning

confidence: 99%

Regio- and Enantioselective Ring-Opening of Epoxides with HMDST: A Straightforward Access to 1,2-Mercaptoalcohols

Degl’Innocenti¹,

Capperucci²,

Cerreti³

et al. 2005

Synlett

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Reaction of 3-phenylglycidic esters. Part 2. Stereo- and regio-selectivity in the oxirane ring opening of methyl trans-3-(4-methoxyphenyl)glycidate with various thiophenols and the effects of solvent and temperature

Cited by 24 publications

References 4 publications

Oxidative Nucleophilic Substitution (S_NOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

Oxidative Nucleophilic Substitution (S_NOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

Catalytic Approaches to Optically Active 1,5-Benzothiazepines

Regio- and Enantioselective Ring-Opening of Epoxides with HMDST: A Straightforward Access to 1,2-Mercaptoalcohols

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Reaction of 3-phenylglycidic esters. Part 2. Stereo- and regio-selectivity in the oxirane ring opening of methyl trans-3-(4-methoxyphenyl)glycidate with various thiophenols and the effects of solvent and temperature

Cited by 24 publications

References 4 publications

Oxidative Nucleophilic Substitution (SNOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

Oxidative Nucleophilic Substitution (SNOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

Catalytic Approaches to Optically Active 1,5-Benzothiazepines

Regio- and Enantioselective Ring-Opening of Epoxides with HMDST: A Straightforward Access to 1,2-Mercaptoalcohols

Contact Info

Product

Resources

About

Oxidative Nucleophilic Substitution (S_NOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

Oxidative Nucleophilic Substitution (S_NOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues