Naked d-orbital in a centrochiral Ni(II) complex as a catalyst for asymmetric [3+2] cycloaddition

Yoshihiro Sohtome (), Genta Nakamura, Atsuya Muranaka, Daisuke Hashizume (), Sylvain Lectard, Teruhisa Tsuchimoto, Masanobu Uchiyama and Mikiko Sodeoka ()
Additional contact information
Yoshihiro Sohtome: Synthetic Organic Chemistry Laboratory, RIKEN
Genta Nakamura: Synthetic Organic Chemistry Laboratory, RIKEN
Atsuya Muranaka: RIKEN Center for Sustainable Resource Science
Daisuke Hashizume: RIKEN Center for Emergent Matter Science
Sylvain Lectard: Synthetic Organic Chemistry Laboratory, RIKEN
Teruhisa Tsuchimoto: School of Science and Technology, Meiji University
Masanobu Uchiyama: RIKEN Center for Sustainable Resource Science
Mikiko Sodeoka: Synthetic Organic Chemistry Laboratory, RIKEN

Nature Communications, 2017, vol. 8, issue 1, 1-10

Abstract: Abstract Chiral metal catalysts have been widely applied to asymmetric transformations. However, the electronic structure of the catalyst and how it contributes to the activation of the substrate is seldom investigated. Here, we report an empirical approach for providing insights into the catalytic activation process in the distorted Ni(II)-catalysed asymmetric [3+2] cycloaddition of α-ketoesters. We quantitatively characterize the bonding nature of the catalyst by means of electron density distribution analysis, showing that the distortion around the Ni(II) centre makes the dz2 orbital partially ‘naked’, wherein the labile acetate ligand is coordinated with electrostatic interaction. The electron-deficient dz2 orbital and the acetate act together to deprotonate the α-ketoester, generating the (Λ)-Ni(II)–enolate. The solid and solution state analyses, together with theoretical calculations, strongly link the electronic structure of the centrochiral octahedral Ni(II) complex and its catalytic activity, depicting a cooperative mechanism of enolate binding and outer sphere hydrogen-bonding activation.

Date: 2017
References: Add references at CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/ncomms14875 Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:8:y:2017:i:1:d:10.1038_ncomms14875

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/ncomms14875

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().