85027-81-2

Upstream product

• 84999-99-5 C₂₂H₂₆O₂ 
• 216306-35-3 (S)-3,3-Dimethyl-2-[(S)-1-((E)-styryl)-but-3-enylamino]-butan-1-ol 
• 216306-34-2 (2S)-3-methyl-2-[(1S)-1-(4-styrylphenyl)but-3-enylamino]butan-1-ol 
• 216306-37-5 (S)-2-Phenyl-2-[(S)-1-((E)-styryl)-but-3-enylamino]-ethanol 
• 216306-38-6 (S)-2-((S,E)-1-phenylhexa-1,5-dien-3-ylamino)-3-phenylpropan-1-ol 
• 3182-95-4 L-Phenylalaninol 
• 84999-94-0 (R)-(-)-cinnamyl 2-methoxy-2-phenylpropyl ether 
• 14371-10-9 (E)-3-phenylpropenal 
• 762-72-1 allyl-trimethyl-silane 
• 127759-27-7 cinnamaldehid-(R)-(+)-α-methylbenzylamine derived imine 
• 637330-73-5 (4S,2'E)-3-(3'-phenylacryloyl)-4-phenyl-5,5-dimethyloxazolidin-2-one 
• 102-92-1 Cinnamoyl chloride 
• 637330-77-9 (3'S,4S)-3-(3'-phenylhex-5-enyl)-4-phenyl-5,5-dimethyloxazolidin-2-one 
• 184483-44-1 (4-Methoxy-phenyl)-((Z)-(S)-3-phenyl-hexa-1,5-dienyl)-carbamic acid tert-butyl ester 

Downstream Products

• 85000-04-0 Acetic acid (S)-3-phenyl-hex-5-enyl ester 
• 501032-71-9 (5S)-1-benzyl-5-phenyl-hexahydro-cyclopenta[c]isoxazole 
• 501032-83-3 (1R,2S,4S)-2-amino-N-benzyl-N-(tert-butoxycarbonyl)-4-phenyl-1-cyclopentanecarboxylic acid 
• 501032-82-2 (1S,2S,4S)-1-amino-N-benzyl-N-(tert-butoxycarbonyl)-2-hydroxymethyl-4-phenylcyclopentane 
• 1025927-97-2 (1R,2S,4S)-2-Benzylamino-4-phenyl-cyclopentanecarboxylic acid 
• 501032-81-1 (1S,2S,4S)-1-amino-N-benzyl-2-hydroxymethyl-4-phenylcyclopentane 
• 501032-84-4 (3S)-6-aza-6-benzyl-3-phenyl-bicyclo[3.2.0]heptan-7-one 
• 127393-00-4 (S)-3-phenylhex-5-enoic acid 

Relevant academic research and scientific papers

A General Organocatalytic System for Enantioselective Radical Conjugate Additions to Enals

Herein, we report a general iminium ion-based catalytic method for the enantioselective conjugate addition of carbon-centered radicals to aliphatic and aromatic enals. The process uses an organic photoredox catalyst, which absorbs blue light to generate radicals from stable precursors, in combination with a chiral amine catalyst, which secures a consistently high level of stereoselectivity. The generality of this catalytic platform is demonstrated by the stereoselective interception of a wide variety of radicals, including non-stabilized primary ones which are generally difficult to engage in asymmetric processes. The system also served to develop organocatalytic cascade reactions that combine an iminium-ion-based radical trap with an enamine-mediated step, affording stereochemically dense chiral products in one-step.

Utilizing the asymmetric amino-cope rearrangement as a novel approach to enantiomerically enriched 3-substituted aldehydes

We report the asymmetric amino-Cope rearrangement of some novel 3-amino-1,5-diene substrates to yield enantiomerically enriched 3-alkyl and 3-aryl aldehyde products. We have developed a system that gives excellent and comparable levels of product enantiomeric excess (ee) for both alkyl-and aryl-substituted products. Our results have implications for the control of the mechanistic pathway of the amino-Cope rearrangement and thus its potential utility in asymmetric synthesis.

Applications of the amino-cope rearrangement: Synthesis of tetrahydropyran, δ-lactone and piperidine targets

We report a novel approach to some chiral tetrahydropyran and δ-lactone targets that utilizes the asymmetric amino-Cope rearrangement as a key synthetic step. Products of amino-Cope rearrangement chemistry have also been applied to access piperidine targe

SuperQuat N-acyl-5,5-dimethyloxazolidin-2-ones for the asymmetric synthesis of α-alkyl and β-alkyl aldehydes

The proclivity of α-branched N-2′-benzyl-3′-phenylpropionyl derivatives of (S)-4-benzyl-5,5-dimethyl-, (S)-4-phenyl-5,5-dimethyl-, (S)-4-isopropyl-5,5-dimethyl-, (S)-4-benzyl- and (S)-4-benzyl-5,5-diphenyl-oxazolidin-2-ones to generate directly 2-benzyl-3-phenylpropionaldehyde upon hydride reduction with DIBAL is investigated. The (S)-4-benzyl-5,5-dimethyl-derivative proved optimal for inhibition of endocyclic nucleophilic attack, giving 2-benzyl-3-phenylpropionaldehyde in good yield upon reduction. Application of this methodology for the asymmetric synthesis of chiral aldehydes via diastereoselective enolate alkylation of a range of (S)-N-acyl-4-benzyl-5,5-dimethyloxazolidin-2-ones to afford an array of α-substituted-N-acyl-5,5-dimethyloxazolidin-2-ones (85-94% de) and subsequent reduction with DIBAL afforded directly non-racemic α-substituted aldehydes without loss of stereochemical integrity (87-94% ee). The extension of this protocol for the asymmetric synthesis of β-substituted aldehydes is demonstrated, via the diastereoselective conjugate addition of a range of organocuprates to (S)-N-acyl-4-phenyl-5,5-dimethyloxazolidin-2-ones which proceeds with high diastereoselectivity (generally >95% de). Reduction of the conjugate addition products with DIBAL gives non-racemic β-substituted aldehydes in high yields and in high ee (generally >95% ee). This methodology is exemplified by the asymmetric synthesis of (R)-3-isopropenylhept-6-enal, which has previously been used in the synthesis of (3Z,6R)-3-methyl-6-isopropenyl-3,9-decadien-1-yl acetate, a component of the sex pheromones of the California red scale.

Synthetic applications of lithiated N-Boc allylic amines as asymmetric homoenolate equivalents

Lithiation of N-(Boc)-N-(p-methoxyphenyl) allylic amines in the presence of (-)-sparteine provides asymmetric homoenolate equivalents which react with electrophiles to provide highly enantioenriched enecarbamates. Acidic hydrolysis of the enecarbamates can provide the corresponding β-substituted aldehydes. A synthetic sequence that involves a stereocontrolled intramolecular nitrone-olefin dipolar cycloaddition has been developed for the preparation of enantioenriched 2-formyl-4-phenyl-1-aminocyclopentanes from one β-allyl-substituted aldehyde. Further manipulations allow access to an enantioenriched β-lactam. In another synthetic sequence, transmetalation of the lithiated intermediates and reactions with aldehyde electrophiles can be controlled to afford highly enantioenriched anti homoaldol products. Use of an anti aldehyde homoaldol product as the chiral electrophile in an iterative reaction provides a double homoaldol product containing four stereogenic centers with high diastereoselectivity and enantioselectivity. Reaction pathways are proposed to account for the observed products.

Synthetic applications of the amino-Cope rearrangement: Enantioselective synthesis of some tetrahydropyrans

We report a novel and enantioselective approach to 2,4-disubstituted tetrahydropyrans that utilises the asymmetric amino-Cope rearrangement as a key synthetic step.

Enantioenriched acid, ester, and ketone β-phenyl homoenolate synthetic equivalents from N-Boc-N-(p-methoxyphenyl)cinnamylamine

Oxidation of the β-substituted highly enantioenriched aldehydes obtained by hydrolysis of the 3,3-disubstituted enecarbamates affords enantioenriched β-substituted acids and esters. Lithiation of enantio-enriched 3,3-disubstituted enecarbamates and subsequent reaction with electrophiles provides vinylically substituted enecarbamates. The use of benzyl and alkyl halide electrophiles affords α-substituted enecarbamates, which can be hydrolyzed to provide enantioenriched β-substituted ketones. Reaction of the lithiated intermediate with ketones affords oxazolidinones, which can be reductively ring-opened with DIBAL and hydrolyzed to provide enantioenriched β-substituted, α'-hydroxy ketones. These transformations demonstrate that the enantioselective lithiation of N-Boc-N-(p-methoxyphenyl)cinnamylamine provides a reactive intermediate which can be a ketone, acid, or ester homoenolate synthon. (C) 2000 Published by Elsevier Science Ltd.

High asymmetric induction in anionic amino-cope rearrangements controlled by β-aminoalcohol auxiliaries

Novel 3-amino-1,5-dienes were prepared with high diastereoselectivity by unprecedented 1,2-addition of allyl Grignard to α,β-unsaturated imines containing β-aminoalcohol auxiliaries. Asymmetric anionic amino-Cope rearrangement of the diastereoisomerically pure 3-amino-1,5-diene substrates proceeded to yield the target 3-substituted aldehyde in good yield and with high levels of asymmetric induction (up to 94% e.e.).

The first example of asymmetric induction in an anionic amino-Cope rearrangement

The anionic amino-Cope rearrangement of suitably functionalized acyclic 3-amino-1,5-diene substrates has been achieved and we report the first example of an asymmetric anionic amino-Cope rearrangement to yield an enantiomerically enriched product (75% e.e.). The absolute stereochemistry of the products has been verified and transition state models are proposed to rationalize the stereochemical outcome.

Chiral Homoenolate Equivalents, II. - Asymmetric Synthesis of 3-Substituted 3-Phenylpropionaldehydes via Metallated Chiral Cinnamylamines

The diastereomeric excess obtained in alkylation reactions of the chiral homoenolate equivalent 22 with prolinol ether as chiral auxiliary leading to the formation of phenylpropionaldehydes 24 depends strongly on the solvent used.The structure of the alkylating reagent on the other hand is not important.The best results (about 9:1) are obtained in tert-butyl methyl ether as solvent.Other chiral auxiliaries testet were uneffective. - Key Words: Chiral homoenolate equivalents / Alkylation / Chiral 1-aminoallyl anions / Chiral aldehydes