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Molecular Engineering of β-Substituted Oxoporphyrinogens for Hydrogen-Bond Donor Catalysis

preprint
submitted on 20.08.2019 and posted on 20.08.2019 by Mandeep K. Chahal, Daniel Payne, Yoshitaka Matsushita, Jan Labuta, Katsuhiko Ariga, Jonathan P. Hill

A new class of bifunctional hydrogen-bond donor organocatalyst using oxoporphyrinogens with increased intramolecular hydrogen-bond donor distances is reported. Oxoporphyrinogens are highly non-planar rigid macrocycles containing a multiple hydrogen bond forming binding site. In this work we report the first example of non-planar OxPs as hydrogen-bond donor catalysts. The introduction of β-substituents is key to the catalytic activity and the catalysts are able to catalyze 1,4-conjugate additions and sulfa-Michael additions, as well as, Henry and aza-Henry reactions at low catalyst loadings (≤ 1 mol%) under mild conditions. Preliminary mechanistic studies have been carried out and a possible reaction mechanism has been proposed based on the bi-functional activation of both substrates through hydrogen-bonding interactions.

Funding

This work was partly supported by World Premier International Research Center Initiative (WPI Initiative), MEXT, Japan. The authors are grateful to Japan Society for the Promotion of Science (JSPS) for a JSPS Fellowship (to D.T.P.). This work was also partially supported by JSPS KAKENHI Grant No. JP16H06518 (Coordination Asymmetry), Grant No. 19K05229, and CREST, JST Grant No. JPMJCR1665.

History

Email Address of Submitting Author

PAYNE.Daniel@nims.go.jp

Institution

National Institute for Materials Science

Country

Japan

ORCID For Submitting Author

0000-0001-7707-8381

Declaration of Conflict of Interest

The authors declare no competing financial interest.

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