Search results for "Stereom"

Regioselective Synthesis of Mono- and Dispiropyrazoline Derivatives via 1,3-dipolar Cycloaddition with Nitrilimines

2016

The 1,3-dipolar cycloaddition reaction of (E,E)-1,3-bis(arylidene)indan-2-one with diarylnitrilimines, generated in situ via dehydrohalogenation of the corresponding hydrazonoyl chlorides , affords predominantly monospiropyrazolines and as a mixture of diastereoisomers. Also dispiropyrazolines are formed in moderate yields. The structure and stereochemistry of cycloadducts were confirmed by 1H and 13C-NMR spectroscopy, elemental analyses data, and single-crystal X-ray diffraction studies of and .

Synthesis of substituted piperidines by enantioselective desymmetrizing intramolecular aza-Michael reactions.

2018

An organocatalytic enantioselective intramolecular aza-Michael reaction has been described for the first time in a desymmetrization process employing substrates different from cyclohexadienones. By using 9-amino-9-deoxy-epi-hydroquinine as the catalyst and trifluoroacetic acid as a co-catalyst, a series of enantiomerically enriched 2,5-and 2,6-disubstituted piperidines have been obtained in good yields and with moderate diastereoselectivity. Depending on the catalyst/co-catalyst loading ratio, either the major or the minor diastereoisomer of the final piperidine products was achieved with high levels of enantioselectivity. Finally, some mechanistic insights have been considered by means of …

Total Synthesis of Stemoamide, 9a-epi-Stemoamide, and 9a,10-epi-Stemoamide: Divergent Stereochemistry of the Final Methylation Steps

2020

Total syntheses of stemoamide, 9a-epi-stemoamide, and 9a,10-epi-stemoamide by a convergent A + B ring-forming strategy is reported. The synthesis required a diastereoselective late-stage methylation of the ABC stemoamide core that successfully enabled access to three of the four possible diastereomeric structures. For the natural stemoamide series, the diastereoselectivity can be rationalized both by kinetic and thermodynamic arguments, whereas for the natural 9a-epi-stemoamide series, the kinetic selectivity is explained by the prepyramidalization of the relevant enolate.

Formation and trapping of the thermodynamically unfavoured inverted-hemicucurbit[6]uril

2019

Amplification of a thermodynamically unfavoured macrocyclic product through the directed shift of the equilibrium between dynamic covalent chemistry library members is difficult to achieve. We show for the first time that during condensation of formaldehyde and cis-N,N'-cyclohexa-1,2-diylurea formation of inverted-cis-cyclohexanohemicucurbit[6]uril (i-cis-cycHC[6]) can be induced at the expense of thermodynamically favoured cis-cyclohexanohemicucurbit[6]uril (cis-cycHC[6]). The formation of i-cis-cycHC[6] is enhanced in low concentration of the templating chloride anion and suppressed in excess of this template. We found that reaction selectivity is governed by the solution-based template-a…

Athenacrinus n. gen. and other early echinoderm taxa inform crinoid origin and arm evolution

2020

AbstractIntermediate morphologies of a new fossil crinoid shed light on the pathway by which crinoids acquired their distinctive arms. Apomorphies originating deep in echinoderm history among early nonblastozoan pentaradiate echinoderms distinguish Tremadocian (earliest Ordovician) crinoid arms from later taxa. The brachial series is separated from the ambulacra, part of the axial skeleton, by lateral plate fields. Cover plates are arrayed in two tiers, and floor plates expressed podial basins and pores. Later during the Early Ordovician, floor plates contacted and nestled into brachials, then were unexpressed as stereom elements entirely and cover plates were reduced to a single tier. Inco…

Addition of thiols to the double bond of dipeptide C-terminal dehydroalanine as a source of new inhibitors of cathepsin C.

2017

Addition of thiols to double bond of glycyl-dehydroalanine and phenyl-dehydroalanine esters provided micromolar inhibitors of cathepsin C. The structure-activity studies indicated that dipeptides containing N-terminal phenylalanine exhibit higher affinity towards the enzyme. A series of C-terminal S-substituted cysteines are responsible for varying interaction with S1 binding pocket of cathepsin C. Depending on diastereomer these compounds most likely act as slowly reacting substrates or competitive inhibitors. This was proved by TLC analysis of the medium in which interaction of methyl (S)-phenylalanyl-(R,S)-(S-adamantyl)cysteinate (7i) with the enzyme was studied. Molecular modeling enabl…

Novel functionalized cispentacin derivatives. Synthesis of 1,2,3-triazole-substituted 2-aminocyclopentanecarboxylate stereoisomers

2008

Four 1,2,3-triazole-substituted ethyl 2-amino-3-hydroxycyclopentanecarboxylate diastereomers (3,4-disubstituted cispentacins) with a cyclopentane skeleton were prepared in enantiomerically pure form from racemic β-lactam 7 via enzymatic ring opening, epoxidation and selective ring opening of the oxirane ring with sodium azide. The formation of the 1,2,3-triazole ring system involved click chemistry: 1,3-dipolar cycloaddition of the corresponding 4-substituted azidocarboxylates with diethyl acetylenedicarboxylate.

Schul-Stereometrie

1883

Development and testing of a tool for learning stereometry at high school: Poster

2021

Aminosäureester als chirale Hilfsgruppen in Lewis-Säure-katalysierten Diels-Alder-Reaktionen

1990

Amino Acid Esters as Chiral Auxiliaries in Lewis Acid Catalyzed Diels-Alder Reactions Cyclopentadiene, cyclohexadiene and alkyl-substituted butadienes react with N-acryloyl-, N-crotonoyl- and N-(4-nitro-cinnamoyl)-(S)-proline benzyl and allyl ester in the presence of Lewis acids to give the cycloadducts in high yields and with stereoselectivities of up to 97:3 for the endo isomers. The sense of the asymmetric induction in these reactions can be directed by the use of differently coordinating catalysts (e.g. TiCl4: (2R):(2S) = 96:4; EtAlCl2: (2R):(2S) = 10:90 at 0°C). In the TiCl4-catalyzed reactions with the fumaric acid derivatives the ratio of the diastereomers reaches values of up to 112…