The Role of Trichloroacetimidate To Enable Iridium-Catalyzed Regio- and Enantioselective Allylic Fluorination: A Combined Experimental and Computational Study.

التفاصيل البيبلوغرافية
العنوان:	The Role of Trichloroacetimidate To Enable Iridium-Catalyzed Regio- and Enantioselective Allylic Fluorination: A Combined Experimental and Computational Study.
المؤلفون:	Sorlin AM; Department of Chemistry , University of Iowa , Iowa City , Iowa 52242 , United States., Mixdorf JC; Department of Chemistry , University of Iowa , Iowa City , Iowa 52242 , United States., Rotella ME; Department of Chemistry and Biochemistry , University of Maryland , College Park , Maryland 20742 , United States., Martin RT; Department of Chemistry and Biochemistry , University of Maryland , College Park , Maryland 20742 , United States., Gutierrez O; Department of Chemistry and Biochemistry , University of Maryland , College Park , Maryland 20742 , United States., Nguyen HM; Department of Chemistry , Wayne State University , Detroit , Michigan 48202 , United States.
المصدر:	Journal of the American Chemical Society [J Am Chem Soc] 2019 Sep 18; Vol. 141 (37), pp. 14843-14852. Date of Electronic Publication: 2019 Sep 09.
نوع المنشور:	Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, Non-P.H.S.
اللغة:	English
بيانات الدورية:	Publisher: American Chemical Society Country of Publication: United States NLM ID: 7503056 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-5126 (Electronic) Linking ISSN: 00027863 NLM ISO Abbreviation: J Am Chem Soc Subsets: PubMed not MEDLINE; MEDLINE
أسماء مطبوعة:	Publication: Washington, DC : American Chemical Society Original Publication: Easton, Pa. [etc.]
مستخلص:	Asymmetric allylic fluorination has proven to be a robust and efficient methodology with potential applications for the development of pharmaceuticals and practical synthesis for ¹⁸ F-radiolabeling. A combined computational (dispersion-corrected DFT) and experimental approach was taken to interrogate the mechanism of the diene-ligated, iridium-catalyzed regio- and enantioselective allylic fluorination. Our group has shown that, in the presence of an iridium(I) catalyst and nucleophilic fluoride source (Et 3 N·3HF), allylic trichloroacetimidates undergo rapid fluoride substitution to generate allylic fluoride products with excellent levels of branched-to-linear ratios. Mechanistic studies reveal the crucial role of the trichloroacetimidate as a potent leaving group and ligand to enable conversion of racemic allylic trichloroacetimidates to the corresponding enantioenriched allylic fluorides, via a dynamic kinetic asymmetric transformation (DYKAT), in the presence of the chiral bicyclo[3.3.0]octadiene-ligated iridium catalyst.
تواريخ الأحداث:	Date Created: 20190824 Date Completed: 20200609 Latest Revision: 20200609
رمز التحديث:	20240628
DOI:	10.1021/jacs.9b07575
PMID:	31438667
قاعدة البيانات:	MEDLINE

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الوصف
تدمد:	1520-5126
DOI:	10.1021/jacs.9b07575