Stereodivergent Rhodium(III)-Catalyzed cis-Cyclopropanation Enabled by Multivariate Optimization.
| Autor: | Piou T; Department of Chemistry , Columbia University , New York , New York , United States 10027., Romanov-Michailidis F; Department of Chemistry , Columbia University , New York , New York , United States 10027., Ashley MA; Department of Chemistry , Columbia University , New York , New York , United States 10027., Romanova-Michaelides M; Department of Biochemistry , University of Geneva , 1211 Geneva 4, Switzerland., Rovis T; Department of Chemistry , Columbia University , New York , New York , United States 10027. |
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| Jazyk: | angličtina |
| Zdroj: | Journal of the American Chemical Society [J Am Chem Soc] 2018 Aug 01; Vol. 140 (30), pp. 9587-9593. Date of Electronic Publication: 2018 Jul 23. |
| DOI: | 10.1021/jacs.8b04243 |
| Abstrakt: | The design of stereodivergent transformations is of great interest to the synthetic community as it allows funneling of a given reaction pathway toward one stereochemical outcome or another by only minor adjustments of the reaction setup. Herein, we present a physical organic approach to invert the sense of induction in diastereoselective cyclopropanation of alkenes with N-enoxyphthalimides through rhodium(III) catalysis. Careful parametrization of catalyst-substrate molecular determinants allowed us to interrogate linear-free energy relationships and establish an intuitive and robust statistical model that correlates an extensive number of data points in high accuracy. Our multivariate correlations-steered mechanistic investigation culminated with a robust and general diastereodivergent cyclopropanation tool where the switch from trans- to cis-diastereoinduction is attributed to a mechanistic dichotomy. Selectivity might be determined by the flexibility of rhodacyclic intermediates derived from ring-opened versus -unopened phthalimides, induced by both their respective ring size and the Sterimol B |
| Databáze: | MEDLINE |
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