Synthesis of Bicyclic Hemiacetals Catalyzed by Unnatural Densely Substituted γ-Dipeptides

Overview

Journal J Org Chem

Publisher American Chemical Society

Specialty Chemistry

Date 2022 Sep 30

PMID 36178434

Authors

Maddalen Agirre

Tamara Bello

Jinxiu Zhou

Maria de Gracia Retamosa

Fernando P Cossio

Affiliations

Soon will be listed here.

Abstract

The asymmetric synthesis of bicyclic highly substituted tetrahydropyrans is described. The reaction is catalyzed by unnatural γ-dipeptides based on densely substituted l- and d-proline derivatives. This organocatalytic one-pot reaction takes place among a ketone, a nitroalkene, and an aldehyde to yield an octahydro-2-chromene scaffold. Monomeric species, from which the corresponding γ-dipeptides are synthesized, cannot catalyze the reaction, thus confirming the emergent nature of the catalytic behavior of these dimeric species.

References

Retamosa M, Ruiz-Olalla A, Bello T, de Cozar A, Cossio F . A Three-Component Enantioselective Cyclization Reaction Catalyzed by an Unnatural Amino Acid Derivative. Angew Chem Int Ed Engl. 2017; 57(3):668-672. DOI: 10.1002/anie.201708952. View

DSouza A, Paknikar S, Dev V, Beauchamp P, Kamat S . Biogenetic-type synthesis of (+)-cymbodiacetal, a constituent of Cymbopogon martinii. J Nat Prod. 2004; 67(4):700-2. DOI: 10.1021/np030338h. View

Ishikawa H, Sawano S, Yasui Y, Shibata Y, Hayashi Y . Asymmetric one-pot four-component coupling reaction: synthesis of substituted tetrahydropyrans catalyzed by diphenylprolinol silyl ether. Angew Chem Int Ed Engl. 2011; 50(16):3774-9. DOI: 10.1002/anie.201005386. View

Vetica F, Chauhan P, Dochain S, Enders D . Asymmetric organocatalytic methods for the synthesis of tetrahydropyrans and their application in total synthesis. Chem Soc Rev. 2017; 46(6):1661-1674. DOI: 10.1039/c6cs00757k. View

Tu W, Wang S, Chien S, Lin F, Chen L, Chiu C . Diterpenes from Cryptomeria japonica inhibit androgen receptor transcriptional activity in prostate cancer cells. Planta Med. 2007; 73(13):1407-9. DOI: 10.1055/s-2007-990233. View

Cutler , Ross , Sayed , Dugan , Bartlett , Hill . Koninginin G, a new metabolite from trichoderma aureoviride . J Nat Prod. 1999; 62(1):137-9. DOI: 10.1021/np9801817. View

Hahn R, Raabe G, Enders D . Asymmetric synthesis of highly functionalized tetrahydropyrans via a one-pot organocatalytic Michael/Henry/ketalization sequence. Org Lett. 2014; 16(14):3636-9. PMC: 4700516. DOI: 10.1021/ol501236a. View

Gurubrahamam R, Cheng Y, Chen K . Control of five contiguous stereogenic centers in an organocatalytic kinetic resolution via Michael/acetalization sequence: synthesis of fully substituted tetrahydropyranols. Org Lett. 2015; 17(3):430-3. DOI: 10.1021/ol5033656. View

Chandrasekhar S, Mallikarjun K, Pavankumarreddy G, Rao K, Jagadeesh B . Enantiopure cycloalkane fused tetrahydropyrans through domino Michael-ketalizations with organocatalysis. Chem Commun (Camb). 2009; (33):4985-7. DOI: 10.1039/b904662c. View

10.

Bachle F, Duschmale J, Ebner C, Pfaltz A, Wennemers H . Organocatalytic asymmetric conjugate addition of aldehydes to nitroolefins: identification of catalytic intermediates and the stereoselectivity-determining step by ESI-MS. Angew Chem Int Ed Engl. 2013; 52(48):12619-23. DOI: 10.1002/anie.201305338. View

11.

Bures J, Armstrong A, Blackmond D . Mechanistic rationalization of organocatalyzed conjugate addition of linear aldehydes to nitro-olefins. J Am Chem Soc. 2011; 133(23):8822-5. DOI: 10.1021/ja203660r. View

12.

Casas J, Engqvist M, Ibrahem I, Kaynak B, Cordova A . Direct amino acid catalyzed asymmetric synthesis of polyketide sugars. Angew Chem Int Ed Engl. 2004; 44(9):1343-5. DOI: 10.1002/anie.200461400. View

13.

Retamosa M, Ruiz-Olalla A, Agirre M, de Cozar A, Bello T, Cossio F . Additive and Emergent Catalytic Properties of Dimeric Unnatural Amino Acid Derivatives: Aldol and Conjugate Additions. Chemistry. 2021; 27(63):15671-15687. PMC: 9293019. DOI: 10.1002/chem.202102394. View

14.

Ruiz-Olalla A, Retamosa M, Cossio F . Densely Substituted L-Proline Esters as Catalysts for Asymmetric Michael Additions of Ketones to Nitroalkenes. J Org Chem. 2015; 80(11):5588-99. DOI: 10.1021/acs.joc.5b00495. View

15.

Uroos M, Lewis W, Blake A, Hayes C . Total synthesis of (+)-cymbodiacetal: a re-evaluation of the biomimetic route. J Org Chem. 2010; 75(24):8465-70. DOI: 10.1021/jo101691n. View