Gosteli−Claisen Rearrangement: Substrate Synthesis, Simple Diastereoselectivity, and Kinetic Studies

Rehbein, Julia; Leick, Sabine; Hiersemann, Martin

doi:10.1021/jo802303m

Cited by 41 publications

(33 citation statements)

References 85 publications

(32 reference statements)

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“…1,1,2‐Ethenetricarboxylic acid 1,1‐diethyl ester 1 was prepared according to the literature . ( Z )‐Cinnamyl alcohol was prepared by hydrogenation of 3‐phenyl‐2‐propyn‐1‐ol with Lindlar catalyst in methanol.…”

Section: Methodsmentioning

confidence: 99%

Intramolecular Cyclization of 3,3‐Diarylpropenylamides of Electron‐Deficient Alkenes: Stereoselective Synthesis of Functionalized Hexahydrobenzo[f]isoindoles

Sugiura

Yamazaki

2018

Eur J Org Chem

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Intramolecular Diels–Alder reactions of various 3,3‐diarylpropenylamides of electron‐deficient alkenes to give hexahydrobenzo[f]isoindoles were investigated. Reaction of 1,1,2‐ethenetricarboxylic acid 1,1‐diethyl ester with 3,3‐diaryl‐2‐propen‐1‐amines under the amide formation conditions gave the tricyclic compounds in sequential processes involving intramolecular Diels–Alder reaction. The reaction gave cis‐ and trans‐fused tricyclic compounds selectively, depending on the substituents on the benzene ring, reaction temperature and solvent. In the reaction with dissymmetrically substituted 3,3‐diaryl‐2‐propen‐1‐amines, trans‐substituted aryl group reacted mainly as a styrene component. Amides of electron‐deficient alkenic carboxylic acids such as fumarate do not undergo cyclization at room temperature sequentially and the reaction on heating gave trans‐fused hexahydrobenzo[f]isoindoles. The origin of the observed stereoselectivity has been examined by the DFT calculations.

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Section: Methodsmentioning

confidence: 99%

Intramolecular Cyclization of 3,3‐Diarylpropenylamides of Electron‐Deficient Alkenes: Stereoselective Synthesis of Functionalized Hexahydrobenzo[f]isoindoles

Sugiura

Yamazaki

2018

Eur J Org Chem

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“…A total of 42 aldol additions of Li enolates of acyclic glycolic acid esters including silyl esters 49 emerged from our search (Scheme 15). [32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51] A broad variety of ester residues R 1 , protecting groups PG, and aldehydes were used. Diastereoselectivities ranged from 50:50 to 83:17 in 39 of the 42 reactions (Scheme 15, top), but surpassed this value only exceptionally (Scheme 15, bottom).…”

Section: Review Syn Thesismentioning

confidence: 99%

Stereoselective Aldol Additions of Glycolic Acid and Its Derivatives

Engesser¹,

Brückner²

2019

Synthesis

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This review gives a comprehensive overview of aldol additions of glycolic acid derivatives to achiral aldehydes and acetals affording α,β-dihydroxycarboxylic acids or derivatives thereof. The focus is on simple diastereoselectivity. A selection of related aldol additions is also presented: aldol additions of glycolic acid derivatives to ketones with two different substituents and aldol additions of α-substituted glycolic acid derivatives.1 Introduction1.1 Organization of this Review1.2 Outside the Scope of this Review: Aldol Additions Giving α,β-Dihydroxyaldehydes and α,β-Dihydroxyketones Diastereoselectively1.3 Non-Aldol Routes to Diastereomerically Pure α,β-Dihydroxycarboxylic Acid Derivatives2 Aldol Additions of Glycolic Acid (Derivative) Enolates to Aldehydes2.1 Aldol Additions of Glycolate Enolates (‘Glycolic Acid Dianions’)2.2 Aldol Additions of Glycolic Ester Enolates2.3 Aldol Additions of Glycolic Thioester Enolates2.4 Aldol Additions of Glycolimide Enolates2.5 Aldol Additions of Glycolamide Enolates2.6 Mukaiyama Aldol Additions of Silyl Ketene Acetals of Glycolic Esters and Thioesters2.7 Aldol Additions of Glycoloyl Chlorides via Acyl Ammonium Enolates3 Aldol-Providing Substitutions of Glycolimide Enolates in Acetals4 Additions Related to Aldol Additions of Glycolic Acid Derivative Enolates to Aldehydes4.1 Selected Simply Diastereoselective Aldol Additions of Enolates of Glycolic Acid Derivatives to Ketones with Two Different Substituents4.2 Simply Diastereoselective Aldol Additions of Enolates of Glycolic Acid Derivatives with a Methyl Substituent at C-α (Lactic Acid Derivatives)5 Conclusion

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“…NaHCO 3 (3 × 10 mL), then dried and concentrated in vacuo. Purification via flash column chromatography (eluent, [30][31][32][33][34][35][36][37][38][39][40]92 : 8) gave 29 as a colourless oil (20 mg, 48% from 25, >99 : 1 dr); [α] 20 D +11.1 (c 1.0 in CHCl 3 ).…”

Section: Methyl (2s3r)-2-(3′-methylbutyl)-3-(n-isopropylamino)-3-phementioning

confidence: 99%

Diastereoselective Ireland–Claisen rearrangements of substituted allyl β-amino esters: applications in the asymmetric synthesis of C(5)-substituted transpentacins

et al. 2014

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The diastereoselective Ireland-Claisen rearrangement of a range of substituted allyl β-amino esters gave the corresponding enantiopure α-substituted-β-amino esters with good diastereoselectivity. The application of this methodology in the asymmetric synthesis of a range of C(5)-substituted 1,2-anti-1,5-syn-transpentacins was demonstrated by the rearrangement of a range of β-amino esters derived from sorbic acid, followed by esterification, ring-closing metathesis, hydrogenolytic deprotection/reduction, and hydrolysis, which gave the C(5)-substituted transpentacins in only 9 steps from commercially available starting materials.

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Gosteli−Claisen Rearrangement: Substrate Synthesis, Simple Diastereoselectivity, and Kinetic Studies

Cited by 41 publications

References 85 publications

Intramolecular Cyclization of 3,3‐Diarylpropenylamides of Electron‐Deficient Alkenes: Stereoselective Synthesis of Functionalized Hexahydrobenzo[f]isoindoles

Intramolecular Cyclization of 3,3‐Diarylpropenylamides of Electron‐Deficient Alkenes: Stereoselective Synthesis of Functionalized Hexahydrobenzo[f]isoindoles

Stereoselective Aldol Additions of Glycolic Acid and Its Derivatives

Diastereoselective Ireland–Claisen rearrangements of substituted allyl β-amino esters: applications in the asymmetric synthesis of C(5)-substituted transpentacins

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