Regioselective and Stereospecific Rhodium-Catalyzed Allylic Cyanomethylation with an Acetonitrile Equivalent: Construction of Acyclic β-Quaternary Stereogenic Nitriles.
| Autor: | Tom MJ; Department of Chemistry, Queen's University, 90 Bader Lane, Kingston ON K7L 3N6, Canada., Evans PA; Department of Chemistry, Queen's University, 90 Bader Lane, Kingston ON K7L 3N6, Canada.; Xiangya School of Pharmaceutical Sciences, Central South University, Changsha 410013, Hunan, P. R. of China. |
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| Jazyk: | angličtina |
| Zdroj: | Journal of the American Chemical Society [J Am Chem Soc] 2020 Jul 15; Vol. 142 (28), pp. 11957-11961. Date of Electronic Publication: 2020 Jul 02. |
| DOI: | 10.1021/jacs.0c02316 |
| Abstrakt: | A highly regioselective and stereospecific rhodium-catalyzed cyanomethylation of tertiary allylic carbonates for the construction of acyclic β-quaternary stereogenic nitriles is described. This protocol represents the first example of a metal-catalyzed allylic substitution reaction using a triorganosilyl-stabilized acetonitrile anion, which permits access to several carbonyl derivatives that are challenging to prepare using conventional pronucleophiles. The synthetic utility of the stereospecific cyanomethylation is further exemplified through the construction of an intermediate utilized in the total synthesis of both (-)-epilaurene and (-)-α-cuparenone. |
| Databáze: | MEDLINE |
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