Palladium-catalyzed Suzuki-Miyaura Cross-coupling Reactions of Enantiomerically Enriched Potassium β-trifluoroboratoamides with Various Aryl- and Hetaryl Chlorides

Overview

Journal Org Lett

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2010 Sep 14

PMID 20831191

Citations 5

Authors

Gary A Molander

Inji Shin

Ludivine Jean-Gerard

Affiliations

Soon will be listed here.

Abstract

Enantiomerically enriched potassium β-trifluoroboratoamides were synthesized as air-stable solids in greater than 95:5 dr using pseudoephedrine as the chiral auxiliary. With these chiral nucleophiles, Suzuki-Miyaura cross-coupling reactions were carried out with various aryl- and hetaryl chlorides in good to excellent yields. Moreover, the diastereoselectivities were preserved throughout the Suzuki-Miyaura cross-coupling reactions.

Citing Articles

α-Arylation/Heteroarylation of Chiral α-Aminomethyltrifluoroborates by Synergistic Iridium Photoredox/Nickel Cross-Coupling Catalysis.

Khatib M, Massarico Serafim R, Molander G Angew Chem Int Ed Engl. 2015; 55(1):254-8.

PMID: 26592731 PMC: 4795823. DOI: 10.1002/anie.201506147.

Enantioselective desymmetrization via carbonyl-directed catalytic asymmetric hydroboration and Suzuki-Miyaura cross-coupling.

Hoang G, Yang Z, Smith S, Pal R, Miska J, Perez D Org Lett. 2015; 17(4):940-3.

PMID: 25642639 PMC: 4385711. DOI: 10.1021/ol503764d.

Mechanistic Insights into Carbonyl-Directed Rhodium-Catalyzed Hydroboration: ab Initio Study of a Cyclic γ,δ-Unsaturated Amide.

Yang Z, Pal R, Hoang G, Zeng X, Takacs J ACS Catal. 2014; 4(3):763-773.

PMID: 24804151 PMC: 3985861. DOI: 10.1021/cs401023j.

γ-Selective directed catalytic asymmetric hydroboration of 1,1-disubstituted alkenes.

Smith S, Hoang G, Pal R, Bani Khaled M, Pelter L, Zeng X Chem Commun (Camb). 2012; 48(100):12180-2.

PMID: 23145431 PMC: 3601746. DOI: 10.1039/c2cc36199j.

Metal-free chlorodeboronation of organotrifluoroborates.

Molander G, Cavalcanti L J Org Chem. 2011; 76(17):7195-203.

PMID: 21812468 PMC: 3162988. DOI: 10.1021/jo201313a.

References

Navarre L, Martinez R, Genet J, Darses S . Access to enantioenriched alpha-amino esters via rhodium-catalyzed 1,4-addition/enantioselective protonation. J Am Chem Soc. 2008; 130(19):6159-69. DOI: 10.1021/ja710691p. View

Molander G, Sandrock D . Potassium trifluoroborate salts as convenient, stable reagents for difficult alkyl transfers. Curr Opin Drug Discov Devel. 2009; 12(6):811-23. PMC: 2908178. View

Lee C, Chou T, Zhang X, Wang Z, Kuduk S, Chappell M . Total synthesis and antitumor activity of 12,13-desoxyepothilone F: an unexpected solvolysis problem at C15, mediated by remote substitution at C21. J Org Chem. 2000; 65(20):6525-33. DOI: 10.1021/jo000617z. View

Molander G, Jean-Gerard L . Scope of the Suzuki-Miyaura cross-coupling reaction of potassium trifluoroboratoketohomoenolates. J Org Chem. 2009; 74(3):1297-303. PMC: 2676431. DOI: 10.1021/jo802453m. View

Sibi M, Tatamidani H, Patil K . Enantioselective rhodium enolate protonations. A new methodology for the synthesis of beta2-amino acids. Org Lett. 2005; 7(13):2571-3. PMC: 2596577. DOI: 10.1021/ol050630b. View

Lu W, Chen Y, Hou X . Iridium-catalyzed highly enantioselective hydrogenation of the C=C bond of alpha, beta-unsaturated ketones. Angew Chem Int Ed Engl. 2008; 47(52):10133-6. DOI: 10.1002/anie.200803872. View

Navarre L, Darses S, Genet J . Tandem 1,4-addition/enantioselective protonation catalyzed by rhodium complexes: efficient access to alpha-amino acids. Angew Chem Int Ed Engl. 2004; 43(6):719-23. DOI: 10.1002/anie.200352518. View

Molander G, Canturk B . Organotrifluoroborates and monocoordinated palladium complexes as catalysts--a perfect combination for Suzuki-Miyaura coupling. Angew Chem Int Ed Engl. 2009; 48(49):9240-61. PMC: 2917751. DOI: 10.1002/anie.200904306. View

Lu S, Bolm C . Highly enantioselective synthesis of optically active ketones by iridium-catalyzed asymmetric hydrogenation. Angew Chem Int Ed Engl. 2008; 47(46):8920-3. DOI: 10.1002/anie.200803709. View

10.

Molander G, Jean-Gerard L . Use of potassium beta-trifluoroborato amides in Suzuki-Miyaura cross-coupling reactions. J Org Chem. 2009; 74(15):5446-50. PMC: 2736348. DOI: 10.1021/jo900968h. View

11.

Frost C, Penrose S, Lambshead K, Raithby P, Warren J, Gleave R . Rhodium-catalyzed conjugate addition-enantioselective protonation: the synthesis of alpha,alpha'-dibenzyl esters. Org Lett. 2007; 9(11):2119-22. DOI: 10.1021/ol070603g. View

12.

Darses S, Genet J . Potassium organotrifluoroborates: new perspectives in organic synthesis. Chem Rev. 2007; 108(1):288-325. DOI: 10.1021/cr0509758. View

13.

Chain W, Myers A . A convenient, NMR-based method for the analysis of diastereomeric mixtures of pseudoephedrine amides. Org Lett. 2007; 9(2):355-7. DOI: 10.1021/ol0628762. View

14.

Li S, Zhu S, Zhang C, Song S, Zhou Q . Iridium-catalyzed enantioselective hydrogenation of alpha,beta-unsaturated carboxylic acids. J Am Chem Soc. 2008; 130(27):8584-5. DOI: 10.1021/ja802399v. View

15.

Prieto M, Mayor S, Rodriguez K, Lloyd-Williams P, Giralt E . Racemization in suzuki couplings: a quantitative study using 4-hydroxyphenylglycine and tyrosine derivatives as probe molecules. J Org Chem. 2007; 72(3):1047-50. DOI: 10.1021/jo0621266. View

16.

Hargrave J, Herbert J, Bish G, Frost C . Rhodium-catalysed addition of organotrialkoxysilanes to alpha-substituted acrylic esters. Org Biomol Chem. 2006; 4(17):3235-41. DOI: 10.1039/b606977k. View

17.

Littke A, Fu G . Palladium-catalyzed coupling reactions of aryl chlorides. Angew Chem Int Ed Engl. 2002; 41(22):4176-211. DOI: 10.1002/1521-3773(20021115)41:22<4176::AID-ANIE4176>3.0.CO;2-U. View

18.

Moss R, Wadsworth K, Chapman C, Frost C . Rhodium catalysed tandem conjugate addition-protonation: an enantioselective synthesis of 2-substituted succinic esters. Chem Commun (Camb). 2004; (17):1984-5. DOI: 10.1039/b406905f. View

19.

Molander G, Petrillo D . Suzuki-Miyaura cross-coupling of potassium trifluoroboratohomoenolates. Org Lett. 2008; 10(9):1795-8. DOI: 10.1021/ol800357c. View

20.

Molander G, Ellis N . Organotrifluoroborates: protected boronic acids that expand the versatility of the Suzuki coupling reaction. Acc Chem Res. 2007; 40(4):275-86. DOI: 10.1021/ar050199q. View