The Synthesis of Novel Oxazolinylphosphinic Esters and Amides and Application to the Cyanosilylation of Aldehydes

Overview

Journal Curr Org Synth

Publisher Bentham Science Publishers

Specialty Chemistry

Date 2017 Apr 18

PMID 28413371

Authors

Mei Luo

Affiliations

Soon will be listed here.

Abstract

A new class of modular functionalized oxazolines are synthesized using a simple, novel one-pot method under inert moisture-free conditions. Then the oxazolines can be further elaborated to phosphine-containing oxazolines. The first step is to synthesize intermediates the reaction of 2 - hydroxybenzonitrile or 2-aminobenzonitrile with chiral amino alcohols, subsequent reactions with phosphine chlorides, providing products in moderate yields. Product structures are fully characterized by NMR, IR, MS and X-Ray analyses. These compounds are found to be highly active catalysts for the cyanosilylation of prochiral benzaldehyde (20-96% yield).

References

Doherty S, Knight J, Smyth C, Harrington R, Clegg W . Asymmetric platinum group metal-catalyzed carbonyl-ene reactions: carbon-carbon bond formation versus isomerization. J Org Chem. 2006; 71(26):9751-64. DOI: 10.1021/jo062023n. View

Rasappan R, Hager M, Gissibl A, Reiser O . Highly enantioselective michael additions of indole to benzylidene malonate using simple bis(oxazoline) ligands: importance of metal/ligand ratio. Org Lett. 2006; 8(26):6099-102. DOI: 10.1021/ol062697k. View

You S, Hou X, Dai L, Yu Y, Xia W . Role of planar chirality of S,N- and P,N-ferrocene ligands in palladium-catalyzed allylic substitutions. J Org Chem. 2002; 67(14):4684-95. DOI: 10.1021/jo016330z. View

Muller C, Pfaltz A . Mass spectrometric screening of chiral catalysts by monitoring the back reaction of quasienantiomeric products: palladium-catalyzed allylic substitution. Angew Chem Int Ed Engl. 2008; 47(18):3363-6. DOI: 10.1002/anie.200705081. View

Meyers A, Price A . The Unique Behavior of a Chiral Binaphthyl Oxazoline in the Presence of Cu(I) and Its Role as a Chiral Catalyst. J Org Chem. 2001; 63(3):412-413. DOI: 10.1021/jo971761w. View

Smidt S, Zimmermann N, Studer M, Pfaltz A . Enantioselective hydrogenation of alkenes with iridium-PHOX catalysts: a kinetic study of anion effects. Chemistry. 2004; 10(19):4685-93. DOI: 10.1002/chem.200400284. View

Trost B, Van Vranken D . Asymmetric Transition Metal-Catalyzed Allylic Alkylations. Chem Rev. 1996; 96(1):395-422. DOI: 10.1021/cr9409804. View

McManus H, Guiry P . Recent developments in the application of oxazoline-containing ligands in asymmetric catalysis. Chem Rev. 2004; 104(9):4151-202. DOI: 10.1021/cr040642v. View

Desimoni G, Faita G, Anker Jorgensen K . C(2)-symmetric chiral bis(oxazoline) ligands in asymmetric catalysis. Chem Rev. 2006; 106(9):3561-651. DOI: 10.1021/cr0505324. View

10.

Dai L, Tu T, You S, Deng W, Hou X . Asymmetric catalysis with chiral ferrocene ligands. Acc Chem Res. 2003; 36(9):659-67. DOI: 10.1021/ar020153m. View

11.

Hargaden G, Guiry P . Recent applications of oxazoline-containing ligands in asymmetric catalysis. Chem Rev. 2009; 109(6):2505-50. DOI: 10.1021/cr800400z. View

12.

Mei L, Hai Z, Jie S, Ming Z, Hao Y, Liang H . Modular synthesis of oxazolines and their derivatives. J Comb Chem. 2009; 11(2):220-7. DOI: 10.1021/cc8001537. View

13.

Yu J, RajanBabu T, Parquette J . Conformationally driven asymmetric induction of a catalytic dendrimer. J Am Chem Soc. 2008; 130(25):7845-7. DOI: 10.1021/ja802308a. View

14.

Evans D, Olhava E, Johnson J, Janey J . Chiral C -Symmetric Cu Complexes as Catalysts for Enantioselective Hetero-Diels-Alder Reactions. Angew Chem Int Ed Engl. 2018; 37(24):3372-3375. DOI: 10.1002/(SICI)1521-3773(19981231)37:24<3372::AID-ANIE3372>3.0.CO;2-K. View

15.

Glos , REISER . Aza-bis(oxazolines): new chiral ligands for asymmetric catalysis. Org Lett. 2000; 2(14):2045-8. DOI: 10.1021/ol005947k. View

16.

Fraile J, Garcia J, Gissibl A, Mayoral J, Pires E, Reiser O . C1-symmetric versus C2-symmetric ligands in enantioselective copper-bis(oxazoline)-catalyzed cyclopropanation reactions. Chemistry. 2007; 13(31):8830-9. DOI: 10.1002/chem.200700681. View

17.

Ghosh A, Mathivanan P, Cappiello J . -Symmetric chiral bis(oxazoline)-metal complexes in catalytic asymmetric synthesis. Tetrahedron Asymmetry. 2018; 9(1):1-45. PMC: 6234853. DOI: 10.1016/S0957-4166(97)00593-4. View

18.

Bedekar A, Koroleva E, Andersson P . Investigation of the Effects of the Structure and Chelate Size of Bis-oxazoline Ligands in the Asymmetric Copper-Catalyzed Cyclopropanation of Olefins: Design of a New Class of Ligands. J Org Chem. 1997; 62(8):2518-2526. DOI: 10.1021/jo962021a. View

19.

McManus H, Guiry P . Coupling of bulky, electron-deficient partners in aryl amination in the preparation of tridentate bis(oxazoline) ligands for asymmetric catalysis. J Org Chem. 2002; 67(24):8566-73. DOI: 10.1021/jo0262558. View

20.

Fu G . Applications of planar-chiral heterocycles as ligands in asymmetric catalysis. Acc Chem Res. 2006; 39(11):853-60. DOI: 10.1021/ar068115g. View