Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Leveraging Trifluoromethylated Benzyl Groups toward the Highly 1,2-Cis-Selective Glucosylation of Reactive Alcohols.

ABSTRACT: Here, we demonstrate that substitution of the benzyl groups of glucosyl imidate donors with trifluoromethyl results in a substantial increase in 1,2-cis-selectivity when activated with TMS-I in the presence of triphenylphosphine oxide. Stereoselectivity is dependent on the number of trifluoromethyl groups (4-trifluoromethylbenzyl vs 3,5-bis-trifluoromethylbenzyl). Particularly encouraging is that we observe high 1,2-cis-selectivity with reactive alcohol acceptors.

SUBMITTER: Njeri DK

PROVIDER: S-EPMC8576833 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Leveraging Trifluoromethylated Benzyl Groups toward the Highly 1,2-Cis-Selective Glucosylation of Reactive Alcohols.

Njeri Dancan K DK Valenzuela Erik Alvarez EA Ragains Justin R JR

Organic letters 20211022 21

Here, we demonstrate that substitution of the benzyl groups of glucosyl imidate donors with trifluoromethyl results in a substantial increase in 1,2-cis-selectivity when activated with TMS-I in the presence of triphenylphosphine oxide. Stereoselectivity is dependent on the number of trifluoromethyl groups (4-trifluoromethylbenzyl vs 3,5-bis-trifluoromethylbenzyl). Particularly encouraging is that we observe high 1,2-cis-selectivity with reactive alcohol acceptors. ...[more]

PMID: 34677075

Similar Datasets

Synthesis of Trifluoromethylated Monoterpene Amino Alcohols.

Project description:For the first time, monoterpene trifluoromethylated β-hydroxy-benzyl-O-oximes were synthesized in 81-95% yields by nucleophilic addition of the Ruppert-Prakash reagent (TMSCF3) to the corresponding β-keto-benzyl-O-oximes based on (+)-nopinone, (-)-verbanone and (+)-camphoroquinone. Trifluoromethylation has been determined to entirely proceed chemo- and stereoselective at the C=O rather than C=N bond. Trifluoromethylated benzyl-O-oximes were reduced to the corresponding α-trifluoromethyl-β-amino alcohols in 82-88% yields. The structure and configuration of the compounds obtained have been established.

| S-EPMC9607099 | biostudies-literature

cis-N,N-Bis(2-hy-droxy-benzyl-idene)cyclo-hexane-1,2-diamine.

Project description:In the title compound, C(20)H(22)N(2)O(2), the cyclo-hexane ring adopts a chair conformation and the two N atoms bonded to salicyl-idene groups are in cis positions. Both hy-droxy groups are involved in intra-molecular O-H⋯N hydrogen bonding and the two benzene rings form a dihedral angle of 60.5 (1)°.

| S-EPMC3239038 | biostudies-literature

One-Pot Multicomponent Coupling Reaction of Catechols, Benzyl Alcohols/Benzyl Methyl Ethers, and Ammonium Acetate toward Synthesis of Benzoxazoles.

Project description:The multicomponent coupling reaction of catechol, ammonium acetate, and benzyl alcohol/benzyl methyl ether in the presence of a Fe(III) catalyst precursor afforded benzoxazole derivatives in good to excellent yields. The notable features of this protocol are abundant availability of the catalyst system, large-scale synthesis, high diversity, and high yields of products.

| S-EPMC8412954 | biostudies-literature

An SN2-Type Strategy toward 1,2-cis-Furanosides.

Project description:The stereoselective construction of 1,2-cis furanosidic linkage is synthetically challenging. A strategy that applies to all furanose types remains elusive. In this work, a solution is developed based on gold catalysis and the deployment of the directing-group-on-leaving-group strategy, where a basic oxazole group in the gold-activated leaving group facilitates the stereoinvertive attack by glycosyl acceptors. In addition to exhibiting good to excellent 1,2-cis selectivities, these furanosylation reactions are high-yielding and mostly complete in 30 min to 2 h. A broad range of 1,2-cis-furanosides is prepared. Although some are uncommon, the ease of access enabled by this approach presents new opportunities to study their applications in medicine and materials research.

| S-EPMC10768845 | biostudies-literature

(S)-(+)-cis-4'-Benzyl-oxypraziquantel.

Project description:The asymmetric unit of the title compound, C26H30N2O3 {systematic name (S)-(+)-2-[cis-4-(benz-yloxy)cyclo-hexa-ne-carb-on-yl]-1,2,3,6,7,11b-hexa-hydro-4H-pyrazino-[2,1-a]isoquin-olin-4-one}, consists of two independent mol-ecules in which the O= Camide group is syn to the N-C(C=Olactam) moiety, making dihedral angles of 2.0 (8) and 3.7 (8)°. The conformation of the 1,4-disubstituted cyclo-hexane ring is cis in each independent mol-ecule, with the carbonyl group occupying an equatorial position and the benz-yloxy group an axial position. In one mol-ecule, two C and one O atom of the benz-yloxy group are disordered over two sets of sites, with a refined occupancy ratio of 0.772 (8):0.228 (8). In the crystal, mol-ecules are linked by C-H⋯O inter-actions, forming ribbons parallel to the b-axis direction.

| S-EPMC3885080 | biostudies-literature

cis-Cyclo-heptane-1,2-diol.

Project description:The title compound, C(7)H(14)O(2), is a vicinal diol derived from cyclo-heptane with cis-orientated hydr-oxy groups. The mol-ecules shows no non-crystallographic symmetry. The O-C-C-O torsion angles of both mol-ecules present in the asymmetric unit [-66.4 (2) and -66.9 (2)°] are similar to those in trans-configured cyclo-hexane derivatives (including pyran-oses) as well as rac-trans-cyclo-heptane-1,2-diol, but smaller than those in trans-configured cyclo-pentane derivatives (including furan-oses). In the crystal structure, O-H⋯O hydrogen bonds furnish the formation of sheets parallel to [110].

| S-EPMC2971971 | biostudies-literature

Stabilization of Glucosyl Dioxolenium Ions by "Dual Participation" of the 2,2-Dimethyl-2-(ortho-nitrophenyl)acetyl (DMNPA) Protection Group for 1,2-cis-Glucosylation.

Project description:The stereoselective introduction of glycosidic bonds is of paramount importance to oligosaccharide synthesis. Among the various chemical strategies to steer stereoselectivity, participation by either neighboring or distal acyl groups is used particularly often. Recently, the use of the 2,2-dimethyl-2-(ortho-nitrophenyl)acetyl (DMNPA) protection group was shown to offer enhanced stereoselective steering compared to other acyl groups. Here, we investigate the origin of the stereoselectivity induced by the DMNPA group through systematic glycosylation reactions and infrared ion spectroscopy (IRIS) combined with techniques such as isotopic labeling of the anomeric center and isomer population analysis. Our study indicates that the origin of the DMNPA stereoselectivity does not lie in the direct participation of the nitro moiety but in the formation of a dioxolenium ion that is strongly stabilized by the nitro group.

| S-EPMC9295149 | biostudies-literature

cis-1-Benzyl-pyrrolidine-2,5-dicarbonitrile.

Project description:In the title compound, C(13)H(13)N(3), the cyano groups at the 2- and 5-positions are eclipsed with each other. The phenyl ring is disordered over two sets of sites, with refined occupancies of 0.520 (5) and 0.480 (5). The angles between the mean plane of the pyrrolidine ring and the two cyano groups are 71.7 (9) and 75.0 (12)°.

| S-EPMC3099760 | biostudies-literature

Deoxyfluorination of alcohols with 3,3-difluoro-1,2-diarylcyclopropenes.

Project description:Aromatic cation activation is a useful strategy to promote deoxyfunctionalization; however, the deoxyfluorination of alcohols with cyclopropenium cation remains an unsolved problem due to the weak nucleophilicity of fluoride ion. Here we report the use of 3,3-difluoro-1,2-diarylcyclopropenes (CpFluors) as easily accessible and reactivity-tunable deoxyfluorination reagents. The electronic nature of CpFluors is critical for fluorination of monoalcohols via alkoxycyclopropenium cations, and CpFluors with electron-rich aryl substituents facilitate the transformation with high efficiency; however, selective monofluorination of 1,2- and 1,3-diols, which proceeds via cyclopropenone acetals, is less dependent on the electronic nature of CpFluors. Moreover, CpFluors are more sensitive to the electronic nature of alcohols than many other deoxyfluorination reagents, thus fluorination of longer diols can be achieved selectively at the relatively electron-rich position. This research not only unveils the first example of deoxyfluorination reagents that contain an all-carbon scaffold, but also sheds light on the divergent reactivity of cyclopropenium cation in deoxyfunctionalization of alcohols.

| S-EPMC5114535 | biostudies-literature

(S)-α-Benzyl-prolinium cis-[(S)-α-benzyl-prolinato]dichloridopalladium(II).

Project description:The title complex salt, (C12H16NO2)[PdCl2(C12H14NO2)], is of inter-est with respect to organic and organometallic catalysis. The compound crystallizes as very small orange-red irregular prisms and the asymmetric unit contains three crystallographically distinct cation-anion pairs. The coordination geometry about the palladium atoms is square-planar with the chloride ligands cis to one another. The structure displays N-H⋯Cl and O-H⋯O hydrogen bonding such that the N-H⋯Cl hydrogen bonds align the cation-anion pairs in a linear fashion along [001], with the O-H⋯O hydrogen bonds connecting these linear strands along [100] and [010].

| S-EPMC3647805 | biostudies-literature