Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and 13C-labeled bidentate phosphorus ligands and metal complexes

Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and 13C-labeled bidentate phosphorus ligands and metal complexes Full article

Journal

Organic chemistry frontiers
ISSN: 2052-4110 , E-ISSN: 2052-4129

Output data

Year: 2023, Volume: 10, Number: 4, Pages: 1022-1033 Pages count : 12 DOI: 10.1039/d2qo01652d

Authors

Lotsman Kristina A. ¹ , Rodygin Konstantin S. ¹ , Skvortsova Irina ¹ , Kutskaya Anastasia M. ¹ , Minyaev Mikhail E. ² , Ananikov Valentine P. ^1,2

Affiliations

1	Institute of Chemistry, Saint Petersburg State University, Universitetskiy pr. 26, Stary Petergof 198504, Russia
2	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, Russia

Stable and easily detectable isotopic labels provide advanced opportunities in a wide range of chemical applications. Highly specific information can be retrieved upon analysis of isotopic label movement from one position to another. The incorporation of isotopic labels into organic molecules is in high demand; however, it may often be rather challenging. The introduction of D and 13C labels is of particular interest due to authentic signals in NMR spectra and the reliable identification of isotopic label positions in target molecules. In this work, a convenient methodology for the introduction of D and 13C labels was developed using calcium carbide as a source of D- and 13C-labeled acetylene and phosphine oxides as substrates. As a result, d4- and 13C2-1,2-bis(phosphine oxide)ethanes were isolated in yields and isotopic purities up to 99%. The resulting phosphine oxides were reduced to the corresponding phosphines, which were used as ligands for the preparation of D-labeled Ni and Pd complexes in 80–96% yields with further characterization by NMR spectroscopy, X-ray and HRMS. The incorporation of D and 13C labels using calcium carbide and acetylene is of key importance since atom-economical addition reactions can be involved with intrinsic opportunity for saving valuable isotopic labels.

Lotsman K.A. , Rodygin K.S. , Skvortsova I. , Kutskaya A.M. , Minyaev M.E. , Ananikov V.P.
Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and 13C-labeled bidentate phosphorus ligands and metal complexes
Organic chemistry frontiers. 2023. V.10. N4. P.1022-1033. DOI: 10.1039/d2qo01652d WOS Scopus OpenAlex

Web of science:	WOS:000913618900001
Scopus:	2-s2.0-85149012255
OpenAlex:	W4317035050

DB	Citing
OpenAlex	12
Scopus	12
Web of science	9