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Diastereoselective Alkylation (diastereoselective + alkylation)

Distribution by Scientific Domains
Chemistry100%
Distribution within Chemistry
Organic Chemistry75%
General & Introductory Chemistry25%

Selected Abstracts

Diastereoselective Alkylation of (Arene)tricarbonylchromium and Ferrocene Complexes Using a Chiral, C2 -Symmetrical 1,2-Diamine as Auxiliary

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 15 2006
Alexandre Alexakis
No abstract is available for this article. [source]

Diastereoselective Alkylation of (Arene)tricarbonylchromium and Ferrocene Complexes Using a Chiral, C2 -Symmetrical 1,2-Diamine as Auxiliary

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 7 2005
Alexandre Alexakis
Abstract The aminal of (benzaldehyde)tricarbonylchromium and en-antiopure bipyrrolidine undergoes diastereoselective ortho -metallation with butyllithium. Quenching with various electrophiles, followed by hydrolysis of the aminal, affords ortho -substituted (benzaldehyde)tricarbonylchromium compounds with high ee (91,99,%). When quenched with Ph2PCl, a new chiral P,N-bidentate ligand is obtained, which shows efficiency in Pd- and Cu-catalysed reactions. The aminal of ferrocenecarbaldehyde could also be formed, but the ortho -deprotonation occurs with only moderate diastereoselectivity (70,%). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Highly Diastereoselective Alkylation of Vicinal Dianions of Chiral Succinic Acid Derivatives: A New General Strategy to (R)-,-Arylmethl-,-butyrolactones.

CHEMINFORM, Issue 36 2004
Manat Pohmakotr
Abstract For Abstract see ChemInform Abstract in Full Text. [source]

Diastereoselective Alkylation and Reduction of ,-Alkoxyacylsilanes: Stereoselective Construction of Three Contiguous Stereogenic Centers.

CHEMINFORM, Issue 6 2004
Mitsunori Honda
Abstract For Abstract see ChemInform Abstract in Full Text. [source]

ChemInform Abstract: Diastereoselective Alkylation of Acetoacetates of Chiral Inductors.

CHEMINFORM, Issue 4 2001
Synthetic Applications.
Abstract ChemInform 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. [source]

An Efficient Asymmetric Synthesis of 2-Substituted 1,4-Benzodiazepin-3-one as a Potential Molecular Scaffold

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 8 2005
Nuria Cabedo
Abstract 2-Substituted 1,4-benzodiazepine-2-one compounds (9,12) were obtained by a highly diastereoselective alkylation of a seven-membered ring benzolactam (8) in the presence of (R)-phenylglycinol as a chiral inductor. The corresponding acid derivative (16) afforded a conformationally constrained structure suitable for preparing peptidomimetic analogues useful as a novel molecular scaffold. After cleavage of the chiral appendage this approach might also lead efficiently to enantiomerically pure 2-substituted benzodiazepines (15). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

The Nonchiral Bislactim Diethoxy Ether as a Highly Stereo-Inducing Synthon for Sterically Hindered, , -Branched , -Amino Acids: A Practical, Large-Scale Route to an Intermediate of the Novel Renin Inhibitor Aliskiren

HELVETICA CHIMICA ACTA, Issue 8 2003
Richard Göschke
The diastereoselective synthesis of the sterically hindered, , -branched , -amino acid derivative (2S,4S)- 24a and its N -[(tert -butoxy)carbonyl](Boc)-protected alcohol (2S,4S)- 19, both key intermediates of a novel class of nonpeptide renin inhibitors such as aliskiren (1), is described. Initially, the analogous methyl ester (2S,4S)- 17 was obtained by alkylation of the chiral Schöllkopf dihydropyrazine (R)- 12a with the dialkoxy-substituted alkyl bromide (R)- 11a, which proceeded with explicitly high diastereofacial selectivity (ds ,98%) to give (2S,5R,2,S)- 13a (Scheme,4), followed by mild acid hydrolysis and N -Boc protection (Scheme,5). Conversely, the complete lack of stereocontrol and poor yields for the reaction of (R)- 11a with the enantiomeric (S)- 12b suggested, in addition to the anticipated shielding effect by the iPr group at C(2) of the auxiliary, steric repulsion between the MeOC(6) and the bulky residues of (R)- 11a in the proposed transition state, which would strongly disfavor both the Si and Re attack of the electrophile (see Fig.). Based on this rationale, alkylation of the readily accessible achiral diethoxy-dihydropyrazine 21 with (R)- 11a was found to provide a 95,:,5 mixture of diastereoisomers (2S,2,S)- 22a and (2R,2,S)- 23a in high yield (Scheme,6), which afforded in two steps and after recrystallization enantiomerically pure (2S,4S)- 24a. Similarly, the stereochemical course for the alkylation reactions of the related alkyl bromides (S)- 28a and (R)- 28b with both (R)- 12a and (S)- 12b as well as with the achiral 21 was investigated (Schemes,7,9). The precursor bromides (R)- 11a, (S)- 11b, (R)- 28a, and (S)- 28b were efficiently synthesized via the diastereoselective alkylation of the Evans 3-isovaleroyloxazolidin-2-ones (R)- 7a and (S)- 7b either with bromide 6 or with benzyl chloromethyl ether, and subsequent standard transformations (Schemes,3 and 7). A practical and economical protocol of the preparation of (2S,4S)- 24a on a multi-100-g scale is given. This is the first report of the application of an achiral dihydropyrazine, i.e., in form of 21, as a highly stereo-inducing synthon providing rapid access to a N -protected , -branched , -amino acid with (2S) absolute configuration. [source]

Total Synthesis of Potent Antitumor Agent (,)-Lasonolide,A: A Cycloaddition-Based Strategy

CHEMISTRY - AN ASIAN JOURNAL, Issue 10 2008

Abstract A detailed account of the enantioselective total synthesis of (,)-lasonolide,A is described. Our initial synthetic route to the top tetrahydropyran ring involved Evans asymmetric alkylation as the key step. Initially, we relied on the diastereoselective alkylation of an ,-alkoxyacetimide derivative containing an ,, stereogenic center and investigated such an asymmetric alkylation reaction. Although alkylation proceeded in good yield, the lack of diastereoselectivity prompted us to explore alternative routes. Our subsequent successful synthetic strategies involved highly diastereoselective cycloaddition routes to both tetrahydropyran rings of lasonolide,A. The top tetrahydropyran ring was constructed stereoselectively by an intramolecular 1,3-dipolar cycloaddition reaction. The overall process constructed a bicyclic isoxazoline, which was later unravelled to a functionalized tetrahydropyran ring as well as a quaternary stereocenter present in the molecule. The lower tetrahydropyran ring was assembled by a Jacobsen catalytic asymmetric hetero-Diels,Alder reaction as the key step. The synthesis also features a Lewis acid catalyzed epoxide opening to form a substituted ether stereoselectively. [source]