Acyl transfer-enabled catalytic asymmetric Michael addition of α-hydroxy-1-indanones to nitroolefins

Abstract

We report herein an enantioselective acyl transfer protocol via electrophile activation. The reaction cascade sequence encompasses dinuclear zinc-catalyzed asymmetric Michael addition, intramolecular cyclization, and retro-Claisen reaction, which leads to a step- and atom-economic approach to a variety of protected cyclic tertiary α-hydroxyketones in good yields with excellent enantioselectivities (24 examples, 56%-82% yield, 1.5-13 dr and 79%-96% ee). Besides, the large-scale synthesis and further transformation of the products demonstrate the effectiveness of this method for organic synthesis.

Keywords

Acyl transfer / retro-Claisen reaction / zinc catalyst / nitroolefins / α-hydroxy-1-indanones

References

[1] Burke HM,Scanlan EM.Exploring chemoselective S-to-N acyl transfer reactions in synthesis and chemical biology.Nat Commun2017;8:15655 PMCID:PMC5458133

[2] Rodriguez J.Acyl transfer strategies as transient activations for enantioselective synthesis.Synthesis2019;51:1923-34

[3] Gao Y,Siau WY,Asymmetric organocatalytic cascade Michael/ hemiketalization/retro-Henry reaction of β.Chem Commun 2011;47:5819-21.

[4] Lu RJ,Wang JJ,Nie SZ.Organocatalytic asymmetric conjugate addition and cascade acyl transfer reaction of α-nitroketones.J Org Chem2011;76:6230-9

[5] Liu Y,Song H,Tang C.Asymmetric organocatalytic cascade Michael/hemiketalization/retro-aldol reaction of 2-[(E)-2-nitrovinyl]phenols with 2,4-dioxo-4-arylbutanoates: A convenient access to chiral α-keto esters.Adv Synth Catal2013;355:2544-9

[6] Zhou J,Wang QL.Organocatalytic asymmetric cascade Michael/hemiketalization/retro-aldol reaction of 3-acetyl-oxindole with β,γ-unsaturated ketoesters catalyzed by bifunctional amino-squaramides.Tetrahedron2014;70:8665-71

[7] Maity R,Sil AK.Organocatalytic asymmetric Michael/hemiketalization/ retro-aldol reaction of α-nitroketones with unsaturated pyrazolones: synthesis of 3-acyloxy pyrazoles.Org Lett2017;19:662-5

[8] Gharui C,Pan SC.Organocatalytic asymmetric domino Michael/acyl transfer reaction between α-nitroketones and in situ-generated ortho-quinone methides: Route to 2-(1-arylethyl)phenols.Adv Synth Catal2018;360:4502-8

[9] Mondal K,SC .Organocatalytic asymmetric domino Michael/acyl transfer reaction between gamma/delta-hydroxyenones and alpha-nitroketones.J Org Chem2018;83:5301-12

[10] Song YX.Bifunctional squaramide-catalysed asymmetric Michael/hemiketalization/retro-aldol reaction of unsaturated thiazolones with α‐nitroketones: Synthesis of chiral 4-acyloxythiazole derivatives.Adv Synth Catal2019;361:5042-9.

[11] Biswas RG,Unhale RA.Organocatalytic asymmetric cascade Michael-acyl transfer reaction between 2-fluoro-1,3-diketones and unsaturated thiazolones: Access to fluorinated 4-acyloxy thiazoles.Org Lett2021;23:6504-9

[12] Roudier M,Quintard A.Enantioselective cascade formal reductive insertion of allylic alcohols into the C(O)-C bond of 1,3-diketones: ready access to synthetically valuable 3-alkylpentanol units.Org Lett2014;16:2802-5

[13] Quintard A.Organo- and Iron(0) Catalysis for an enantioselective michael addition-hemiketalization-fragmentation sequence to protected ω-hydroxy-nitroketones.Adv Synth Catal2016;358:3362-7.

[14] Zhu Y,Luo S.Asymmetric retro-Claisen reaction by chiral primary amine catalysis.J Am Chem Soc2016;138:3978-81

[15] Han Y,Luo S.Asymmetric retro-Claisen reaction by synergistic chiral primary amine/palladium catalysis.Org Lett2019;21:7258-61

[16] Han Y,Luo S.Highly stereoselective construction of β, β-diaryl-α-branched ketones by the chiral primary amine-catalyzed asymmetric retro-Claisen reaction.Org Lett2022;24:1752-6

[17] Yi ZY,Chang X,Wang CJ.Iridium-catalyzed asymmetric cascade allylation/retro-Claisen reaction.J Am Chem Soc2022;144:20025-34

[18] Zhou Y,Rodriguez J.Enantioselective organocatalytic four-atom ring expansion of cyclobutanones: synthesis of benzazocinones.Angew Chem Int Ed Engl2019;58:456-60

[19] Yang WL,Yang ZT.Organocatalytic regiodivergent ring expansion of cyclobutanones for the enantioselective synthesis of azepino[1,2-a]indoles and cyclohepta[b]indoles.Org Lett2020;22:4026-32

[20] Yang WL,Li W.Diastereo- and enantioselective synthesis of eight-membered heterocycles via an allylation/ring expansion sequence enabled by multiple catalysis.ACS Catal2021;11:12557-64.

[21] Zhang MM,Xiong W,Lu LQ.A dipolar cyclization/fragmentation strategy for the catalytic asymmetric synthesis of chiral eight-membered lactams.CCS Chem2022;4:2620-9.

[22] Parida C,Chandra Sahoo S.α-Nitro-β, β-unsaturated ketones: An electrophilic acyl transfer reagent in catalytic asymmetric friedel-crafts and Michael reactions.Org Lett2019;21:6700-4

[23] Yang WP,Liu TT,Wang MC.Dinuclear zinc-catalyzed asymmetric [3 + 2] cyclization reaction for direct assembly of chiral α-amino-γ-butyrolactones bearing three stereocenters.Org Chem Front2021;8:6998-7003

[24] Han JJ,Mei GJ,Jia SK.Zinc-catalyzed asymmetric [3 + 2] annulations for the construction of chiral spiro[1-indanone-γ-butyrolactones] via a C-N bond cleavage process.Org Chem Front2022;9:5819-24

[25] Pellissier H.Recent developments in enantioselective zinc-catalyzed transformations.Coord Chem Rev2021;439:213926

[26] Trost BM,Mata G.Dinuclear metal-prophenol catalysts: Development and synthetic applications.Angew Chem Int Ed Engl2020;59:4240-61

[27] Cambridge Crystallographic Data Centre. CCDC 2097558 for the major isomer of 3f. Available from: https://www.ccdc.cam.ac.uk/ [Last accessed on 24 Mar 2023]