Dataset Information

Chiral phosphoric acid catalyzed addition of dihydropyrans to N-acyl imines: stereocontrolled access to enantioenriched spirocyclic oxazoletetrahydropyrans with three contiguous stereocenters.

ABSTRACT: Dihydropyran derivatives readily undergo addition to N-acyl imines in the presence of chiral phosphoric acids. This addition process yields an attractive product that is capable of a tandem oxidative-cyclization via an epoxide intermediate.

SUBMITTER: Li G

PROVIDER: S-EPMC2863994 | biostudies-literature | 2010 May

REPOSITORIES: biostudies-literature

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Publications

Chiral phosphoric acid catalyzed addition of dihydropyrans to N-acyl imines: stereocontrolled access to enantioenriched spirocyclic oxazoletetrahydropyrans with three contiguous stereocenters.

Li Guilong G Kaplan Matthew J MJ Wojtas Lukasz L Antilla Jon C JC

Organic letters 20100501 9

Dihydropyran derivatives readily undergo addition to N-acyl imines in the presence of chiral phosphoric acids. This addition process yields an attractive product that is capable of a tandem oxidative-cyclization via an epoxide intermediate. ...[more]

PMID: 20361794

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Project description:A density functional theory (DFT) study is reported to examine the asymmetric transfer hydrogenation (ATH) of imines catalyzed by an indium metal-organic framework (In-MOF) derived from a chiral phosphoric acid (CPA). It is revealed that the imine and reducing agent (i.e., thiazoline) are simultaneously adsorbed on the CPA through H-bonding to form an intermediate, subsequently, a proton is transferred from thiazoline to imine. The transition state TS-R and TS-S are stabilized on the CPA via H-bonding. Compared to the TS-S, the TS-R has shorter H-bonding distances and longer C-H···π distances, it is more stable and experiences less steric hindrance. Consequently, the TS-R exhibits a lower activation barrier affording to the (R)-enantiomer within 68.1% ee in toluene. Imines with substituted groups such as -NO2, -F, and -OCH3 are used to investigate the substitution effects on the ATH. In the presence of an electron-withdrawing group like -NO2, the electrophilicity of imine is enhanced and the activation barrier is decreased. The non-covalent interactions and activation-strain model (ASM) analysis reveal that the structural distortions and the differential noncovalent interactions of TSs in a rigid In-MOF provide the inherent driving force for enantioselectivity. For -OCH3 substituted imine, the TS-S has the strongest steric hindrance, leading to the highest enantioselectivity. When the solvent is changed from toluene to dichloromethane, acetonitrile, and dimethylsulfoxide with increasing polarity, the activation energies of transition state increase whereas their difference decreases. This implies the reaction is slowed down and the enantioselectivity becomes lower in a solvent of smaller polarity. Among the four solvents, toluene turns out to be the best for the ATH. The calculated results in this study are in fairly good agreement with experimental observations. This study provides a mechanistic understanding of the reaction mechanism, as well as substitution and solvent effects on the activity and enantioselectivity of the ATH. The microscopic insights are useful for the development of new chiral MOFs toward important asymmetric reactions.

Dataset Information

Chiral phosphoric acid catalyzed addition of dihydropyrans to N-acyl imines: stereocontrolled access to enantioenriched spirocyclic oxazoletetrahydropyrans with three contiguous stereocenters.

Publications

Chiral phosphoric acid catalyzed addition of dihydropyrans to N-acyl imines: stereocontrolled access to enantioenriched spirocyclic oxazoletetrahydropyrans with three contiguous stereocenters.

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