Doctor of Philosophy, Harvard University (2016)
Carolyn Bertozzi, Postdoctoral Faculty Sponsor
- Lewis acid enhancement by hydrogen-bond donors for asymmetric catalysis Science 2017; 358: 761-764
- Catalytic 1,3-Difunctionalization via Oxidative C–C Bond Activation Journal of the American Chemical Society 2017; 139 (27): 9152-9155
Catalytic, asymmetric difluorination of alkenes to generate difluoromethylated stereocenters
2016; 353 (6294): 51-54
View details for DOI 10.1126/science.aaf8078
- Catalytic, Diastereoselective 1,2-Difluorination of Alkenes Journal of the American Chemical Society 2016; 138 (15): 5000-5003
Chemoselective pd-catalyzed oxidation of polyols: synthetic scope and mechanistic studies.
Journal of the American Chemical Society
2013; 135 (20): 7593-7602
The regio- and chemoselective oxidation of unprotected vicinal polyols with [(neocuproine)Pd(OAc)]2(OTf)2 (1) (neocuproine = 2,9-dimethyl-1,10-phenanthroline) occurs readily under mild reaction conditions to generate α-hydroxy ketones. The oxidation of vicinal diols is both faster and more selective than the oxidation of primary and secondary alcohols; vicinal 1,2-diols are oxidized selectively to hydroxy ketones, whereas primary alcohols are oxidized in preference to secondary alcohols. Oxidative lactonization of 1,5-diols yields cyclic lactones. Catalyst loadings as low as 0.12 mol % in oxidation reactions on a 10 g scale can be used. The exquisite selectivity of this catalyst system is evident in the chemoselective and stereospecific oxidation of the polyol (S,S)-1,2,3,4-tetrahydroxybutane [(S,S)-threitol] to (S)-erythrulose. Mechanistic, kinetic, and theoretical studies revealed that the rate laws for the oxidation of primary and secondary alcohols differ from those of diols. Density functional theory calculations support the conclusion that β-hydride elimination to give hydroxy ketones is product-determining for the oxidation of vicinal diols, whereas for primary and secondary alcohols, pre-equilibria favoring primary alkoxides are product-determining. In situ desorption electrospray ionization mass spectrometry (DESI-MS) revealed several key intermediates in the proposed catalytic cycle.
View details for DOI 10.1021/ja4008694
View details for PubMedID 23659308