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Synthesis 2023; 55(06): 934-944
DOI: 10.1055/a-1948-3003
special topic
Synthetic Advancements Enabled by Phosphorus Redox Chemistry

Two-Step Transesterification of Phosphates, Phosphorothioates, and Phosphonates with a Binaphthyl Group for the Synthesis of P-Chirogenic Phosphates and Phosphonates

Chikako Endo
a   Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan
,
Yurika Inoue
a   Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan
,
Toshifumi Maruyama
a   Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan
,
Mao Minoura
b   Department of Chemistry, College of Science, Rikkyo University, Nishi-ikebukuro, Toshima-ku, Tokyo, 171-8501, Japan
,
Toshiaki Murai∗
a   Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan
› Author AffiliationsThis research was partly supported by a Grant-in-Aid for Scientific Research (C) (22K05109) and (B) (19H02712) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.
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Abstract

Two-step transesterification of four-coordinate pentavalent organophosphorus compounds with a binaphthyl group has been studied in detail. The first step involves transfer of the axial chirality of a ­hydroxybinaphthyl group to the central chirality of the phosphorus atom. The second step is the substitution reaction of P-chirogenic compounds with a hydroxybinaphthyl group with lithium alkoxides, leading to the formation of P-chirogenic phosphates and phosphonates with primary and secondary alkoxy groups.

Key words

P–O bond formation - transesterification - P-chirogenic phosphates - P-chirogenic phosphonates - axis-to-center chirality transfer

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1948-3003.
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Publication History

Received: 22 July 2022

Accepted: 21 September 2022

Accepted Manuscript online:
21 September 2022

Article published online:
03 November 2022

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