Chiral Allylic Amines Research Articles

Allylic amine formation by imination of allylic tellurides

The imination of allylic phenyl tellurides with [N-(ptoluenesulfonyl)imino]phenyliodinane or chloramine-T affords the corresponding allylic amines via [2,3]sigmatropic rearrangement of the tellurimide intermediates in high yields. Application to chiral cinnamyl 2-(1-dimethylaminoethyl)ferrocenyl telluride results in the formation of the corresponding chiral allylic amine, 3-phenyl-3-tosylaminopropene, with 93% ee.

Allylic Amine Formation by Imination of Allylic Tellurides

The imination of allylic phenyl tellurides with [N-(ptoluenesulfonyl)imino]phenyliodinane or chloramine-T affords the corresponding allylic amines via [2,3]sigmatropic rearrangement of the tellurimide intermediates in high yields. Application to chiral cinnamyl 2-(1-dimethylaminoethyl)ferrocenyl telluride results in the formation of the corresponding chiral allylic amine, 3-phenyl-3-tosylaminopropene, with 93% ee.

High chirality transfer in chiral selenimides via[2,3]sigmatropic rearrangement

The imination of chiral cinnamyl 2-(1-dimethylaminoethyl)ferrocenyl selenides with [N-(toluene-p-sulfonyl)imino]-phenyliodinane and chloramine-T affords the corresponding chiral allylic amines via[2,3]sigmatropic rearrangement of the selenimide intermediates with up to 87% ee, highly diastereoselective imination of selenides and highly stereospecific [2,3]sigmatropic rearrangement being shown.

Stereoselective synthesis of protected amino alkyl epoxides

The mechanism of epoxidation of chiral allyl amines has been investigated. The intrinsic stereoselectivity for epoxidation is shown to be approximately 5:1 and is independent of the nitrogen substituent. However, the nature of the N-protecting group influences the stability of the undesired epoxide to the acidic media, with the minor diastereomer undergoing preferential decomposition. Conditions are reported for the highly stereoselective synthesis of epoxide 9R, an important building block in the synthesis of several enzyme inhibitors.

Tandem [3,3]-Sigmatropic Rearrangements in an Ansamycin: Stereospecific Conversion of an (S)-Allylic Alcohol to an (S)-Allylic Amine Derivative

Ansamycin ring modifications in the geldanamycin oncogene inhibitor series were investigated. A carbamate to urea interchange was accomplished with net retention at the 7(S)-center of a geldanamycin analog. This chirally specific transformation was efficiently accomplished by employing tandem [3,3]-sigmatropic rearrangement involving first, the conversion of the allylic 7(S)-alcohol 2b to an allylic 9(S)-thiol, 4b, and then the rearrangement to the allylic 7(S)-isothiocyanate 6, which was carried on to allylic 7(S)-amine derivatives 1a and 1b. This tandem rearrangement strategy may have wide applicability for the preparation of chiral allylic amines from the large array of readily available chiral allylic alcohols

ChemInform Abstract: Diastereoselective and Regioselective Photooxygenation of a Chiral Allylic Amine and Its Acyl Derivatives: Stereochemical Evidence for a Steering Effect by the Amino Group in the Ene Reaction of Singlet Oxygen.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Diastereoselective and regioselective photooxygenation of a chiral allylic amine and its acyl derivatives: stereochemical evidence for a steering effect by the amino group in the ene reaction of singlet oxygen

Diastereoselective and regioselective photooxygenation of a chiral allylic amine and its acyl derivatives: stereochemical evidence for a steering effect by the amino group in the ene reaction of singlet oxygen

ChemInform Abstract: Regio‐ and Stereoselective Hydroboration of Chiral Allylamines. Synthesis of Amino Alcohols.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Regio- and stereoselective hydroborations of chiral allyl amines. Synthesis of amino alcohols

Chiral allyl amines with the carboncarbon double bond at an internal position undergo regio- and stereocontrolled hydroborations to provide 1,2-amino alcohols in good yields. The precursor olefins are readily available from a nucleophilic alaninol synthon prepared from serine.

ChemInform Abstract: On Catalyzed and Uncatalyzed Hydroborations of Chiral Allylic Alcohols and Amines.

AbstractThe allylic acetates (I) and (IV) are hydroxylated via reaction with catecholborane in the presence of a rhodium catalyst, followed by oxidative work‐up, to give mainly the anti‐isomers (III) or (VI) of 1,3‐diols.

A Convenient and Versatile Synthesis of Chiral Aliphatic and Allylic Amines

Preparation of optically pure aliphatic and allylic amines from amino acids is described. Wittig olefination of α-Boc-amino aldehydes affords Boc-protected allylic amines which can be deprotected to the corresponding chiral unsaturated amines. Catalytic reduction of the Wittig product prior to deprotection affords aliphatic amines of high optical purity.

On catalyzed and uncatalyzed hydroborations of chiral allylic alcohols and amines

A model for predicting the sense of diastereoselection in catalyzed hydroborations of allylic alcohol and allylic amine derivatives is discussed.

ChemInform Abstract: CHIRAL HOMOENOLATE EQUIVALENTS. I. ASYMMETRIC SYNTHESIS OF β‐SUBSTITUTED D ALDEHYDES VIA METALATED CHIRAL ALLYLAMINES

Chemischer InformationsdienstVolume 11, Issue 46 Isocyclic Compounds ChemInform Abstract: CHIRAL HOMOENOLATE EQUIVALENTS. I. ASYMMETRIC SYNTHESIS OF β-SUBSTITUTED D ALDEHYDES VIA METALATED CHIRAL ALLYLAMINES H. AHLBRECHT, H. AHLBRECHTSearch for more papers by this authorG. BONNET, G. BONNETSearch for more papers by this authorD. ENDERS, D. ENDERSSearch for more papers by this authorG. ZIMMERMANN, G. ZIMMERMANNSearch for more papers by this author H. AHLBRECHT, H. AHLBRECHTSearch for more papers by this authorG. BONNET, G. BONNETSearch for more papers by this authorD. ENDERS, D. ENDERSSearch for more papers by this authorG. ZIMMERMANN, G. ZIMMERMANNSearch for more papers by this author First published: November 18, 1980 https://doi.org/10.1002/chin.198046191Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume11, Issue46November 18, 1980 RelatedInformation

Chiral homoenolate equivalents. I. Asymmetric synthesis of β-substituted aldehydes via metalated chiral allylamines

Metalated chiral allylamines of type 2 (M = Li, K) are used as chiral homoenolate equivalents and allow after alkylation and acidic hydrolysis asymmetric CC bond formations to β-substituted aldehydes in enantiomeric excesses up to 67%.