Organocatalytic Enantioselective γ-Position-Selective Mannich Reactions of β-Ketocarbonyl Derivatives

Overview

Journal Org Lett

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2022 Sep 12

PMID 36096488

Authors

Venkati Bethi

Fujie Tanaka

Affiliations

Soon will be listed here.

Abstract

Catalytic asymmetric Mannich reactions of β-ketocarbonyl derivatives (such as β-ketoesters and (2-oxopropyl)phosphonate), resulting in the formation of a C-C bond at the γ-position of the β-ketocarbonyl derivatives with high enantioselectivities, are reported. The bond formation at the α-position of the β-ketoester was reversible, and the γ-position-reacted product δ-amino β-ketoester derivative was kinetically formed and was stable. The dynamic kinetic process was key for the direct access to the γ-position-reacted products from β-ketocarbonyls under catalytic conditions.

Citing Articles

Facile construction of distal and diversified tertiary and quaternary stereocenters.

Liu C, Ge R, Chen J, Guo H, Bartholome T, Maiti D Proc Natl Acad Sci U S A. 2024; 121(51):e2408541121.

PMID: 39665763 PMC: 11665887. DOI: 10.1073/pnas.2408541121.

1,3-Diamine-Derived Catalysts: Design, Synthesis, and the Use in Enantioselective Mannich Reactions of Ketones.

Garg Y, Osborne J, Vasylevskyi S, Velmurugan N, Tanaka F J Org Chem. 2023; 88(15):11096-11101.

PMID: 37460110 PMC: 10407930. DOI: 10.1021/acs.joc.3c01051.

References

Melchiorre P . Cinchona-based primary amine catalysis in the asymmetric functionalization of carbonyl compounds. Angew Chem Int Ed Engl. 2012; 51(39):9748-70. DOI: 10.1002/anie.201109036. View

Cai M, Xu K, Li Y, Nie Z, Zhang L, Luo S . Chiral Primary Amine/Ketone Cooperative Catalysis for Asymmetric α-Hydroxylation with Hydrogen Peroxide. J Am Chem Soc. 2021; 143(2):1078-1087. DOI: 10.1021/jacs.0c11787. View

Malerich J, Hagihara K, Rawal V . Chiral squaramide derivatives are excellent hydrogen bond donor catalysts. J Am Chem Soc. 2008; 130(44):14416-7. PMC: 2701638. DOI: 10.1021/ja805693p. View

Deng Q, Xu H, Yuen A, Xu Z, Che C . Ruthenium-catalyzed one-pot carbenoid N-H insertion reactions and diastereoselective synthesis of prolines. Org Lett. 2008; 10(8):1529-32. DOI: 10.1021/ol800087p. View

You Y, Zhang L, Cui L, Mi X, Luo S . Catalytic Asymmetric Mannich Reaction with N-Carbamoyl Imine Surrogates of Formaldehyde and Glyoxylate. Angew Chem Int Ed Engl. 2017; 56(44):13814-13818. DOI: 10.1002/anie.201707005. View

Mondal S, Aher R, Bethi V, Lin Y, Taniguchi T, Monde K . Control of Reactions of Pyruvates by Catalysts: Direct Enantioselective Mannich Reactions of Pyruvates Catalyzed by Amine-based Catalyst Systems. Org Lett. 2022; 24(9):1853-1858. DOI: 10.1021/acs.orglett.2c00436. View

Hamashima Y, Sasamoto N, Hotta D, Somei H, Umebayashi N, Sodeoka M . Catalytic asymmetric addition of beta-ketoesters to various imines by using chiral palladium complexes. Angew Chem Int Ed Engl. 2005; 44(10):1525-9. DOI: 10.1002/anie.200462202. View

Griggs S, Thompson N, Tape D, Fabre M, Clarke P . A Two-Step Synthesis of 2-Spiropiperidines. Chemistry. 2017; 23(39):9262-9265. DOI: 10.1002/chem.201702467. View

Davis F, Theddu N, Gaspari P . Asymmetric synthesis of substituted tropinones using the intramolecular mannich cyclization reaction and acyclic N-sulfinyl beta-amino ketone ketals. Org Lett. 2009; 11(7):1647-50. PMC: 2753232. DOI: 10.1021/ol9002948. View

10.

Liu H, Wu H, Luo Z, Shen J, Kang G, Liu B . Regioselectivity-reversed asymmetric aldol reaction of 1,3-dicarbonyl compounds. Chemistry. 2012; 18(38):11899-903. DOI: 10.1002/chem.201201874. View

11.

Zhang D, Chen Y, Cai H, Yin L, Zhong J, Man J . Direct Catalytic Asymmetric Synthesis of Oxindole-Derived δ-Hydroxy-β-ketoesters by Aldol Reactions. Org Lett. 2019; 22(1):6-10. DOI: 10.1021/acs.orglett.9b03527. View

12.

Cui X, Duan H, Zhang Y, Wang Y . Asymmetric Mannich Reaction of Aryl Methyl Ketones with Cyclic Imines Benzo[e][1,2,3]oxathiazine 2,2-Dioxides Catalyzed by Cinchona Alkaloid-based Primary Amines. Chem Asian J. 2016; 11(21):3118-3125. DOI: 10.1002/asia.201601149. View

13.

Zhang D, Tanaka F . Determination of Relative Frequency of Carbanion Formation at α-Positions of Ketones under Aldol Reaction Catalysis Conditions. Org Lett. 2017; 19(14):3803-3806. DOI: 10.1021/acs.orglett.7b01676. View

14.

Hatano M, Horibe T, Ishihara K . Chiral lithium(I) binaphtholate salts for the enantioselective direct Mannich-type reaction with a change of syn/anti and absolute stereochemistry. J Am Chem Soc. 2009; 132(1):56-7. DOI: 10.1021/ja909874b. View

15.

Song J, Wang Y, Deng L . The Mannich reaction of malonates with simple imines catalyzed by bifunctional cinchona alkaloids: enantioselective synthesis of beta-amino acids. J Am Chem Soc. 2006; 128(18):6048-9. PMC: 3172002. DOI: 10.1021/ja060716f. View

16.

Denmark S, Heemstra Jr J, Beutner G . Catalytic, enantioselective, vinylogous aldol reactions. Angew Chem Int Ed Engl. 2005; 44(30):4682-98. DOI: 10.1002/anie.200462338. View

17.

Clarke P, Zaytsev A, Morgan T, Whitwood A, Wilson C . One-pot synthesis of functionalized piperid-4-ones: a four-component condensation. Org Lett. 2008; 10(13):2877-80. DOI: 10.1021/ol801051g. View

18.

Lou S, Taoka B, Ting A, Schaus S . Asymmetric Mannich reactions of beta-keto esters with acyl imines catalyzed by cinchona alkaloids. J Am Chem Soc. 2005; 127(32):11256-7. DOI: 10.1021/ja0537373. View

19.

Davis F, Fang T, Goswami R . Asymmetric synthesis of substituted prolines from delta-amino beta-ketoesters. Methyl (2S,5R)-(+)-5-phenylpyrrolidine-2-carboxylate. Org Lett. 2002; 4(9):1599-602. DOI: 10.1021/ol025831j. View

20.

Govender T, Arvidsson P, Maguire G, Kruger H, Naicker T . Enantioselective Organocatalyzed Transformations of β-Ketoesters. Chem Rev. 2016; 116(16):9375-437. DOI: 10.1021/acs.chemrev.6b00156. View