Asymmetric Nucleophilic Catalysis with an Octahedral Chiral-at-Metal Iridium(III) Complex

Asymmetric Nucleophilic Catalysis with an Octahedral Chiral-at-Metal Iridium(III) Complex Full article

Journal

ACS Catalysis
ISSN: 2155-5435

Output data

Year: 2017, Volume: 7, Number: 8, Pages: 5151-5162 Pages count : 12 DOI: 10.1021/acscatal.7b01296

Authors

Cruchter Thomas ¹ , Medvedev Michael G. ^2,3 , Shen Xiaodong ¹ , Mietke Thomas ¹ , Harms Klaus ¹ , Marsch Michael ¹ , Meggers Eric ¹

Affiliations

1	Fachbereich#R#Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35043 Marburg, Germany
2	N.D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prospect 47, 119991 Moscow, Russian Federation
3	X-ray Structural Laboratory, A.N. Nesmeyanov Institute of Organoelement Compounds RAS, Vavilova St. 28, 119991 Moscow, Russian Federation

Herein, we report about the design, synthesis, and application of a nucleophilic octahedral chiral-only-at-metal iridium(III) complex. We demonstrate that the enantiopure form of this complex serves as an efficient catalyst for the asymmetric Steglich rearrangement of O-acylated azlactones (up to 96% ee and 99% yield) and the related asymmetric Black rearrangement of O-acylated benzofuranones (up to 94% ee and 99% yield). We provide insight into the mechanisms of these two acyl migration reactions and the catalyst’s manner of chiral recognition with crystal structures of the active catalyst and a catalysis intermediate analog, as well as with quantum chemical calculations based on them. Furthermore, we demonstrate that the presented catalyst also efficiently catalyzes the asymmetric reaction between aryl alkyl ketenes and 2-cyanopyrrole to give the corresponding α-chiral N-acyl pyrroles (up to 95% ee and 99% yield).

Cruchter T. , Medvedev M.G. , Shen X. , Mietke T. , Harms K. , Marsch M. , Meggers E.
Asymmetric Nucleophilic Catalysis with an Octahedral Chiral-at-Metal Iridium(III) Complex
ACS Catalysis. 2017. V.7. N8. P.5151-5162. DOI: 10.1021/acscatal.7b01296 WOS Scopus OpenAlex

≡ Web of science:	WOS:000407309100026
≡ Scopus:	2-s2.0-85027250819
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