Synthesis of Bicyclo[1.1.1]pentane (BCP)-Based Straight-Shaped Diphosphine Ligands

Hideaki Takano; Hitomi Katsuyama; Hiroki Hayashi; Miyu Harukawa; Makoto Tsurui; Sunao Shoji; Yasuchika Hasegawa; Satoshi Maeda; Tsuyoshi Mita

doi:10.1002/anie.202303435

Synthesis of Bicyclo[1.1.1]pentane (BCP)-Based Straight-Shaped Diphosphine Ligands

Angew Chem Int Ed Engl. 2023 Jun 5;62(23):e202303435. doi: 10.1002/anie.202303435. Epub 2023 Apr 20.

Authors

Hideaki Takano^{1

2}, Hitomi Katsuyama^{1

2}, Hiroki Hayashi^{1

2}, Miyu Harukawa³, Makoto Tsurui³, Sunao Shoji^{1

3}, Yasuchika Hasegawa^{1

3}, Satoshi Maeda^{1

2

4

5}, Tsuyoshi Mita^{1

2}

Affiliations

¹ Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21, Nishi 10, Kita-ku, Sapporo, Hokkaido, 001-0021, Japan.
² JST, ERATO Maeda Artificial Intelligence in Chemical Reaction Design and Discovery Project, Kita 10, Nishi 8, Kita-ku, Sapporo, Hokkaido, 060-0810, Japan.
³ Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-Ku, Sapporo, Hokkaido, 060-8628, Japan.
⁴ Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10, Nishi 8, Kita-ku, Sapporo, Hokkaido, 060-0810, Japan.
⁵ Research and Services Division of Materials Data and Integrated System (MaDIS), National Institute for Materials Science (NIMS), Tsukuba, Ibaraki, 305-0044, Japan.

PMID: 36961369
DOI: 10.1002/anie.202303435

Abstract

[1.1.1]Propellane, which is structurally simple and compact, exhibits promising potential for the synthesis of disubstituted straight-shaped bicyclo[1.1.1]pentane (BCP) compounds by manipulation of its highly reactive internal C-C bond. BCPs are considered to be isosteres of 1,4-disubstituted benzenes, which have found broad applications in the areas of functional molecules and drug discovery. The internal C-C single bond of [1.1.1]propellane is regarded as a charge-shift bond, which can be readily cleaved by radical means to construct BCPs. We herein report a novel synthetic method for (un)symmetric diphosphines based on the BCP motif, which can be interpreted as isosteres of 1,4-bis(diphenylphosphino)benzenes. The obtained BCP-diphosphine derivatives were used to generate a straight-shaped Au complex and an Eu-based coordination polymer.

Keywords: Bicyclo[1.1.1]pentane; LED; Phosphines; Photocatalyst; Propellane.

Abstract

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