A new asymmetric catalytic propargyl- and allylboration of hydrazonoesters is reported. The reactions utilize allenyl- and allylboronic acids in the presence of the inexpensive parent BINOL catalyst. The reactions can be performed under mild conditions (0 °C) without any metal catalyst or other additives affording sterically encumbered chiral α-amino acids. This is the first metal-free method for the asymmetric propargyl- and allylboration of hydrazonoesters.
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http://dx.doi.org/10.1039/c8cc07908k | DOI Listing |
J Org Chem
October 2020
Institute for Molecular Design and Synthesis, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, China.
In this study, we disclose the catalytic addition of bi(cyclopentyl)diol-derived boronates to aldehydes promoted by chiral phosphoric acids, allowing for the formation of enantioenriched homoallylic, propargylic, and crotylic alcohols (up to >99% enantiomeric excess (ee), diastereomeric ratio (dr) >20:1). These boronate substrates provided superior enantioselectivities, allowing for the reactions to proceed with low catalyst loading (0.5-5 mol %) and reduced reaction time (15 min at room temperature for aldehyde allylboration).
View Article and Find Full Text PDFChem Commun (Camb)
November 2018
Department of Organic Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden.
A new asymmetric catalytic propargyl- and allylboration of hydrazonoesters is reported. The reactions utilize allenyl- and allylboronic acids in the presence of the inexpensive parent BINOL catalyst. The reactions can be performed under mild conditions (0 °C) without any metal catalyst or other additives affording sterically encumbered chiral α-amino acids.
View Article and Find Full Text PDFNat Commun
December 2017
School of Chemistry and Chemical Engineering and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, 200240, China.
Heterogeneous catalysts typically lack the specific steric control and rational electronic tuning required for precise asymmetric catalysis. Here we demonstrate that a phosphonate metal-organic framework (MOF) platform that is robust enough to accommodate up to 16 different metal clusters, allowing for systematic tuning of Lewis acidity, catalytic activity and enantioselectivity. A total of 16 chiral porous MOFs, with the framework formula [M L (solvent)] that have the same channel structures but different surface-isolated Lewis acid metal sites, are prepared from a single phosphono-carboxylate ligand of 1,1'-biphenol and 16 different metal ions.
View Article and Find Full Text PDFOrg Lett
February 2013
Institut des Sciences Chimiques de Rennes, UMR 6626 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France.
The reactions of 1-silyl-3-boryl-2-alkenes with various electrophilic reagents (Selectfluor, N-halosuccinimides, benzhydryl, and propargylic alcohols in the presence of a Lewis acid, N-alkoxycarbonyliminium ion) have been investigated as new routes to α-substituted allylboronates. Further functional transformations, including allylboration, Suzuki coupling, protodeboronation, and cycloisomerization, have been carried out to illustrate the synthetic potential of these γ-borylallylsilanes.
View Article and Find Full Text PDFJ Org Chem
February 2013
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
The chiral BINOL-phosphoric acid catalyzed allylboration and propargylation reactions are studied with density functional theory (B3LYP and B3LYP-D3). Two different models were recently proposed for these reactions by Goodman and our group, respectively. In Goodman's model for allylborations, the catalyst interacts with the boronate pseudoaxial oxygen.
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