Pentaphosphaferrocene-mediated Synthesis of Asymmetric Organo-phosphines Starting from White Phosphorus

Overview

Journal Nat Commun

Specialty Biology

Date 2021 Oct 2

PMID 34599185

Citations 9

Authors

Stephan Reichl

Eric Madl

Felix Riedlberger

Martin Piesch

Gabor Balazs

Michael Seidl

Manfred Scheer

Affiliations

Soon will be listed here.

Abstract

The synthesis of phosphines is based on white phosphorus, which is usually converted to PCl, to be afterwards substituted step by step in a non-atomic efficient manner. Herein, we describe an alternative efficient transition metal-mediated process to form asymmetrically substituted phosphines directly from white phosphorus (P). Thereby, P is converted to [Cp*Fe(η-P)] (1) (Cp* = η-C(CH)) in which one of the phosphorus atoms is selectively functionalized to the 1,1-diorgano-substituted complex [Cp*Fe(η-PR'R″)] (3). In a subsequent step, the phosphine PR'R″R‴ (R' ≠ R″ ≠ R‴ = alky, aryl) (4) is released by reacting it with a nucleophile R‴M (M = alkali metal) as racemates. The starting material 1 can be regenerated with P and can be reused in multiple reaction cycles without isolation of the intermediates, and only the phosphine is distilled off.

Citing Articles

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References

Guo H, Fan Y, Sun Z, Wu Y, Kwon O . Phosphine Organocatalysis. Chem Rev. 2018; 118(20):10049-10293. PMC: 6218176. DOI: 10.1021/acs.chemrev.8b00081. View

Lee , Yang , PARR . Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B Condens Matter. 1988; 37(2):785-789. DOI: 10.1103/physrevb.37.785. View

Grimme S, Ehrlich S, Goerigk L . Effect of the damping function in dispersion corrected density functional theory. J Comput Chem. 2011; 32(7):1456-65. DOI: 10.1002/jcc.21759. View

Sheldrick G . SHELXT - integrated space-group and crystal-structure determination. Acta Crystallogr A Found Adv. 2014; 71(Pt 1):3-8. PMC: 4283466. DOI: 10.1107/S2053273314026370. View

Butovskiy M, Balazs G, Bodensteiner M, Peresypkina E, Virovets A, Sutter J . Ferrocene and pentaphosphaferrocene: a comparative study regarding redox chemistry. Angew Chem Int Ed Engl. 2013; 52(10):2972-6. DOI: 10.1002/anie.201209329. View

Clevenger A, Stolley R, Aderibigbe J, Louie J . Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis. Chem Rev. 2020; 120(13):6124-6196. DOI: 10.1021/acs.chemrev.9b00682. View

Scott D, Cammarata J, Schimpf M, Wolf R . Synthesis of monophosphines directly from white phosphorus. Nat Chem. 2021; 13(5):458-464. DOI: 10.1038/s41557-021-00657-7. View

Lennert U, Arockiam P, Streitferdt V, Scott D, Rodl C, Gschwind R . Direct catalytic transformation of white phosphorus into arylphosphines and phosphonium salts. Nat Catal. 2019; 2(12):1101-1106. PMC: 6914361. DOI: 10.1038/s41929-019-0378-4. View

Geeson M, Cummins C . Phosphoric acid as a precursor to chemicals traditionally synthesized from white phosphorus. Science. 2018; 359(6382):1383-1385. DOI: 10.1126/science.aar6620. View

10.

Montchamp J . Phosphinate chemistry in the 21st century: a viable alternative to the use of phosphorus trichloride in organophosphorus synthesis. Acc Chem Res. 2013; 47(1):77-87. DOI: 10.1021/ar400071v. View

11.

Pyykko P, Atsumi M . Molecular double-bond covalent radii for elements Li-E112. Chemistry. 2009; 15(46):12770-9. DOI: 10.1002/chem.200901472. View

12.

Sheldrick G . Crystal structure refinement with SHELXL. Acta Crystallogr C Struct Chem. 2015; 71(Pt 1):3-8. PMC: 4294323. DOI: 10.1107/S2053229614024218. View

13.

Hoidn C, Maier T, Trabitsch K, Weigand J, Wolf R . [3+2] Fragmentation of a Pentaphosphido Ligand by Cyanide. Angew Chem Int Ed Engl. 2019; 58(52):18931-18936. PMC: 6972699. DOI: 10.1002/anie.201908744. View

14.

Weigend F, Ahlrichs R . Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Phys Chem Chem Phys. 2005; 7(18):3297-305. DOI: 10.1039/b508541a. View

15.

Mandla K, Neville M, Moore C, Rheingold A, Figueroa J . Dianionic Mononuclear Cyclo-P Complexes of Zero-Valent Molybdenum: Coordination of the Cyclo-P Dianion in the Absence of Intramolecular Charge Transfer. Angew Chem Int Ed Engl. 2019; 58(43):15329-15333. DOI: 10.1002/anie.201908885. View

16.

Tang W, Zhang X . New chiral phosphorus ligands for enantioselective hydrogenation. Chem Rev. 2003; 103(8):3029-70. DOI: 10.1021/cr020049i. View

17.

Arockiam P, Lennert U, Graf C, Rothfelder R, Scott D, Fischer T . Versatile Visible-Light-Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts. Chemistry. 2020; 26(69):16374-16382. PMC: 7756875. DOI: 10.1002/chem.202002646. View

18.

Karl D . Aquatic ecology. Phosphorus, the staff of life. Nature. 2000; 406(6791):31, 33. DOI: 10.1038/35017683. View

19.

Pyykko P, Atsumi M . Molecular single-bond covalent radii for elements 1-118. Chemistry. 2008; 15(1):186-97. DOI: 10.1002/chem.200800987. View

20.

Riegel S, Burford N, Lumsden M, Decken A . Synthesis and characterization of elusive cyclo-di- and -tri-phosphino-1,3-diphosphonium salts: fundamental frameworks in catena-organophosphorus chemistry. Chem Commun (Camb). 2007; (44):4668-70. DOI: 10.1039/b707741f. View