Functional-group-tolerant, Nickel-catalyzed Cross-coupling Reaction for Enantioselective Construction of Tertiary Methyl-bearing Stereocenters

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2013 Jun 12

PMID 23751004

Citations 38

Authors

Hanna M Wisniewska

Elizabeth C Swift

Elizabeth R Jarvo

Affiliations

Soon will be listed here.

Abstract

The first Negishi nickel-catalyzed stereospecific cross-coupling reaction of secondary benzylic esters is reported. A series of traceless directing groups is evaluated for ability to promote cross-coupling with dimethylzinc. Esters with a chelating thioether derived from commercially available 2-(methylthio)acetic acid are most effective. The products are formed in high yield and with excellent stereospecificity. A variety of functional groups are tolerated in the reaction including alkenes, alkynes, esters, amines, imides, and O-, S-, and N-heterocycles. The utility of this transformation is highlighted in the enantioselective synthesis of a retinoic acid receptor agonist and a fatty acid amide hydrolase inhibitor.

Citing Articles

Deoxygenative radical cross-coupling of C(sp)-O/C(sp)-H bonds promoted by hydrogen-bond interaction.

Wang Y, Zhang S, Zeng K, Zhang P, Song X, Chen T Nat Commun. 2024; 15(1):6745.

PMID: 39117625 PMC: 11310525. DOI: 10.1038/s41467-024-50897-7.

Combretastatins D series and analogues: from isolation, synthetic challenges and biological activities.

de Lima Neto J, Menezes P Beilstein J Org Chem. 2023; 19:399-427.

PMID: 37025497 PMC: 10071520. DOI: 10.3762/bjoc.19.31.

Expedient Access to Underexplored Chemical Space: Deoxygenative C(sp)-C(sp) Cross-Coupling.

Lyon W, MacMillan D J Am Chem Soc. 2023; 145(14):7736-7742.

PMID: 36975797 PMC: 10680137. DOI: 10.1021/jacs.3c01488.

A bifunctional amino acid to study protein-protein interactions.

Yang T, Li X, Li X RSC Adv. 2022; 10(69):42076-42083.

PMID: 35516754 PMC: 9057919. DOI: 10.1039/d0ra09110c.

Deaminative Reductive Methylation of Alkylpyridinium Salts.

Bercher O, Plunkett S, Mortimer T, Watson M Org Lett. 2021; 23(18):7059-7063.

PMID: 34464140 PMC: 8448964. DOI: 10.1021/acs.orglett.1c02458.

References

Palani A, Shapiro S, Josien H, Bara T, Clader J, Greenlee W . Synthesis, SAR, and biological evaluation of oximino-piperidino-piperidine amides. 1. Orally bioavailable CCR5 receptor antagonists with potent anti-HIV activity. J Med Chem. 2002; 45(14):3143-60. DOI: 10.1021/jm0200815. View

Barreiro E, Kummerle A, Fraga C . The methylation effect in medicinal chemistry. Chem Rev. 2011; 111(9):5215-46. DOI: 10.1021/cr200060g. View

Johnson D, Ahn K, Kesten S, Lazerwith S, Song Y, Morris M . Benzothiophene piperazine and piperidine urea inhibitors of fatty acid amide hydrolase (FAAH). Bioorg Med Chem Lett. 2009; 19(10):2865-9. PMC: 3150822. DOI: 10.1016/j.bmcl.2009.03.080. View

Swift E, Jarvo E . Asymmetric transition metal-catalyzed cross-coupling reactions for the construction of tertiary stereocenters. Tetrahedron. 2013; 69(29):5799-5817. PMC: 3743270. DOI: 10.1016/j.tet.2013.05.001. View

Wu K, Zhou S, Chen C, Yang M, Chiang R, Chen C . Instantaneous room-temperature and highly enantioselective ArTi(O-i-Pr)3 additions to aldehydes. Chem Commun (Camb). 2011; 47(42):11668-70. DOI: 10.1039/c1cc15059f. View

Bolm C, Rudolph J . Catalyzed asymmetric aryl transfer reactions to aldehydes with boronic acids as aryl source. J Am Chem Soc. 2002; 124(50):14850-1. DOI: 10.1021/ja028518l. View

Swanson D, Dubin A, Shah C, Nasser N, Chang L, Dax S . Identification and biological evaluation of 4-(3-trifluoromethylpyridin-2-yl)piperazine-1-carboxylic acid (5-trifluoromethylpyridin-2-yl)amide, a high affinity TRPV1 (VR1) vanilloid receptor antagonist. J Med Chem. 2005; 48(6):1857-72. DOI: 10.1021/jm0495071. View

Wagner A, Rychnovsky S . Determination of absolute configuration of secondary alcohols using thin-layer chromatography. J Org Chem. 2013; 78(9):4594-8. PMC: 3702370. DOI: 10.1021/jo400432q. View

Leung C, Leung S, Tirado-Rives J, Jorgensen W . Methyl effects on protein-ligand binding. J Med Chem. 2012; 55(9):4489-500. PMC: 3353327. DOI: 10.1021/jm3003697. View

10.

Roth B, Blankley C, Chucholowski A, Ferguson E, Hoefle M, Ortwine D . Inhibitors of cholesterol biosynthesis. 3. Tetrahydro-4-hydroxy-6-[2-(1H-pyrrol-1-yl)ethyl]-2H-pyran-2-one inhibitors of HMG-CoA reductase. 2. Effects of introducing substituents at positions three and four of the pyrrole nucleus. J Med Chem. 1991; 34(1):357-66. DOI: 10.1021/jm00105a056. View

11.

Choi J, Fu G . Catalytic asymmetric synthesis of secondary nitriles via stereoconvergent Negishi arylations and alkenylations of racemic α-bromonitriles. J Am Chem Soc. 2012; 134(22):9102-5. PMC: 3415582. DOI: 10.1021/ja303442q. View

12.

Braga A, Paixao M, Westermann B, Schneider P, Wessjohann L . Acceleration of arylzinc formation and its enantioselective addition to aldehydes by microwave irradiation and aziridine-2-methanol catalysts. J Org Chem. 2008; 73(7):2879-82. DOI: 10.1021/jo702413n. View

13.

Pamies O, Andersson P, Dieguez M . Asymmetric hydrogenation of minimally functionalised terminal olefins: an alternative sustainable and direct strategy for preparing enantioenriched hydrocarbons. Chemistry. 2010; 16(48):14232-40. DOI: 10.1002/chem.201001909. View

14.

Nave S, Sonawane R, Elford T, Aggarwal V . Protodeboronation of tertiary boronic esters: asymmetric synthesis of tertiary alkyl stereogenic centers. J Am Chem Soc. 2010; 132(48):17096-8. DOI: 10.1021/ja1084207. View

15.

Fischer C, Fu G . Asymmetric nickel-catalyzed Negishi cross-couplings of secondary alpha-bromo amides with organozinc reagents. J Am Chem Soc. 2005; 127(13):4594-5. DOI: 10.1021/ja0506509. View

16.

Rousseau G, Breit B . Removable directing groups in organic synthesis and catalysis. Angew Chem Int Ed Engl. 2011; 50(11):2450-94. DOI: 10.1002/anie.201006139. View

17.

Schadendorf D, Worm M, Jurgovsky K, Dippel E, Michel S, Charpentier B . Retinoic Acid receptor-gamma-selective retinoids exert antiproliferative effects on human-melanoma cell-growth in-vitro. Int J Oncol. 2011; 5(6):1325-31. DOI: 10.3892/ijo.5.6.1325. View

18.

Giovannini R, Studemann T, Devasagayaraj A, Dussin G, Knochel P . New Efficient Nickel-Catalyzed Cross-Coupling Reaction between Two Csp(3) Centers. J Org Chem. 2001; 64(10):3544-3553. DOI: 10.1021/jo982317b. View

19.

Zhou Q, Srinivas H, Dasgupta S, Watson M . Nickel-catalyzed cross-couplings of benzylic pivalates with arylboroxines: stereospecific formation of diarylalkanes and triarylmethanes. J Am Chem Soc. 2013; 135(9):3307-10. PMC: 4218864. DOI: 10.1021/ja312087x. View

20.

Pereira A, Strangman W, Marion F, Feldberg L, Roll D, Mallon R . Synthesis of phosphatidylinositol 3-kinase (PI3K) inhibitory analogues of the sponge meroterpenoid liphagal. J Med Chem. 2010; 53(24):8523-33. DOI: 10.1021/jm100531u. View