3 research outputs found
Stereocontrolled Synthesis of Substituted Chiral Piperidines via One-Pot Asymmetric 6π-Azaelectrocyclization: Asymmetric Syntheses of (−)-Dendroprimine, (+)-7-Epidendroprimine, (+)-5-Epidendroprimine, and (+)-5,7-Epidendroprimine
The asymmetric one-pot 6Ï€-azaelectrocyclization
of alkenyl
vinyl stannane, ethyl (<i>Z</i>)-2-iodo-4-oxobutenoate,
and (−)-7-isopropyl-<i>cis</i>-aminoindanol in the
presence of a Pd(0) catalyst stereoselectively produced the tetracyclic
aminoacetal compounds, resulting from the four-bond formation accompanying
by controlling the stereochemistry at the two asymmetric centers.
The produced cyclic aminoacetals can be regarded as synthetic precursors
of substituted chiral piperidines, and the syntheses of 2,4- and 2,4,6-substituted
piperidines were realized from the obtained aminoacetals by the stereoselective
hydrogenation of the double bond conjugated with the C-4 ester group
and alkylation at the aminoacetal moiety. In addition, the stereoselective
synthesis of an indolizidine alkaloid, (−)-dendroprimine, and
its three stereoisomers, (+)-7-epidendroprimine, (+)-5-epidendroprimine,
and (+)-5,7-epidendroprimine, were achieved
Stereocontrolled Synthesis of Substituted Chiral Piperidines via One-Pot Asymmetric 6π-Azaelectrocyclization: Asymmetric Syntheses of (−)-Dendroprimine, (+)-7-Epidendroprimine, (+)-5-Epidendroprimine, and (+)-5,7-Epidendroprimine
The asymmetric one-pot 6Ï€-azaelectrocyclization
of alkenyl
vinyl stannane, ethyl (<i>Z</i>)-2-iodo-4-oxobutenoate,
and (−)-7-isopropyl-<i>cis</i>-aminoindanol in the
presence of a Pd(0) catalyst stereoselectively produced the tetracyclic
aminoacetal compounds, resulting from the four-bond formation accompanying
by controlling the stereochemistry at the two asymmetric centers.
The produced cyclic aminoacetals can be regarded as synthetic precursors
of substituted chiral piperidines, and the syntheses of 2,4- and 2,4,6-substituted
piperidines were realized from the obtained aminoacetals by the stereoselective
hydrogenation of the double bond conjugated with the C-4 ester group
and alkylation at the aminoacetal moiety. In addition, the stereoselective
synthesis of an indolizidine alkaloid, (−)-dendroprimine, and
its three stereoisomers, (+)-7-epidendroprimine, (+)-5-epidendroprimine,
and (+)-5,7-epidendroprimine, were achieved
Crystal Engineering of Self-Assembled Porous Protein Materials in Living Cells
Crystalline
porous materials have been investigated for development
of important applications in molecular storage, separations, and catalysis.
The potential of protein crystals is increasing as they become better
understood. Protein crystals have been regarded as porous materials
because they present highly ordered 3D arrangements of protein molecules
with high porosity and wide range of pore sizes. However, it remains
difficult to functionalize protein crystals in living cells. Here,
we report that polyhedra, a natural crystalline protein assembly of
polyhedrin monomer (PhM) produced in insect cells infected by cypovirus,
can be engineered to extend porous networks by deleting selected amino
acid residues located on the intermolecular contact region of PhM.
The adsorption rates and quantities of fluorescent dyes stored within
the mutant crystals are increased relative to those of the wild-type
polyhedra crystal (WTPhC) under both <i>in vitro</i> and <i>in vivo</i> conditions. These results provide a strategy for
designing self-assembled protein materials with applications in molecular
recognition and storage of exogenous substances in living cell as
well as an entry point for development of bioorthogonal chemistry
and <i>in vivo</i> crystal structure analysis