Stereochemical Outcome of Copper-Catalyzed C鈥揌 Insertion Reactions. An Experimental and Theoretical Study
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- 作者：Gonzalo Jim茅nez-Os茅s ; Eugenio Vispe ; Marta Rold谩n ; Sergio Rodr铆guez-Rodr铆guez ; Pilar L贸pez-Ram-de-Viu ; Luis Salvatella ; Jos茅 A. Mayoral ; Jos茅 M. Fraile
- 刊名：The Journal of Organic Chemistry
- 出版年：2013
- 出版时间：June 21, 2013
- 年：2013
- 卷：78
- 期：12
- 页码：5851-5857
- 全文大小：405K
- 年卷期：v.78,no.12(June 21, 2013)
- ISSN：1520-6904
文摘
The combination of chiral preparative HPLC separation, VCD measurements, and theoretical calculations allows the unambiguous determination of the absolute configuration of the conformationally flexible products of copper-catalyzed carbene insertion reactions. DFT calculations were used to predict the stereochemical outcome of the copper-bis(oxazoline)-catalyzed C鈥揌 insertion reaction between methyl diazophenylacetate and tetrahydrofuran and also to predict the absolute configuration of the major stereoisomers derived from the same reaction with different cyclic ethers. These predictions were verified experimentally through NMR and VCD spectroscopy and allowed rationalization of the stereochemical outcome of these reactions without further derivatization of the products, which can be prblematic under certain conditions as described herein.