Abstract
AbstractHydrogen borrowing catalysis serves as a powerful alternative to enolate alkylation, enabling the direct coupling of ketones with unactivated alcohols. However, to date, methods that enable control over the absolute stereochemical outcome of such a process have remained elusive. Here we report a catalytic asymmetric method for the synthesis of enantioenriched cyclohexanes from 1,5‐diols via hydrogen borrowing catalysis. This reaction is mediated by the addition of a chiral iridium(I) complex, which is able to impart high levels of enantioselectivity upon the process. A series of enantioenriched cyclohexanes have been prepared and the mode of enantioinduction has been probed by a combination of experimental and DFT studies.
Highlights
Reactions were carried out in flame-dried glassware under an atmosphere of nitrogen unless stated otherwise
Electron impact ionisation (EI) HRMS were performed on an Agilent 7200 quadrupole time of flight (Q-ToF) instrument equipped with a direct insertion probe supplied by Scientific Instrument Manufacturer (SIM) GmbH
Purification via column chromatography eluting with 95:5 pentane/Et2O afforded the title compound 1 as a white solid (12.0 g, 93%)
Summary
Reactions were carried out in flame-dried glassware under an atmosphere of nitrogen unless stated otherwise. Electrospray ionisation (ESI) HRMS were recorded on a Thermo Exactive orbitrap spectrometer equipped with a Waters Equity LC system, with a flow rate of 0.2 mL/min using water:methanol:formic acid (10:89.9:0.1) as eluent. Electron impact ionisation (EI) HRMS were performed on an Agilent 7200 quadrupole time of flight (Q-ToF) instrument equipped with a direct insertion probe supplied by Scientific Instrument Manufacturer (SIM) GmbH. The mass reported is that containing the most abundant isotopes, with each value to 4 decimal places and within 5 ppm of the calculated mass. Reverse phase HPLC was performed on a Dionex UltiMate 3000 system equipped with UV-vis variable wavelength detector, fitted with an Agilent InfinityLab Poroshell 120 EC-C18 column (0.46 cm ø x 150 mm, 4 μm pore size)
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