TY - JOUR

T1 - Access to Spiro Bis-β-lactams via a Metal-Free Microwave-Assisted Wolff Rearrangement/Staudinger [2+2] Cycloaddition Cascade Involving 3-Diazotetramic Acids and Imines

AU - Krivovicheva, V.

AU - Lyutin, I.

AU - Kantin, G.

AU - Dar’in, D.

N1 - Export Date: 11 March 2024 CODEN: JOCEA Адрес для корреспонденции: Dar’in, D.; Saint Petersburg State UniversityRussian Federation; эл. почта: d.dariin@spbu.ru Сведения о финансировании: Russian Science Foundation, RSF, 20-13-00024 Текст о финансировании 1: The authors are grateful to the Russian Science Foundation for financial support (Project Grant 20-13-00024). The authors thank the Research Centre for Magnetic Resonance, the Center for Chemical Analysis and Materials Research, and the Centre for X-ray Diffraction Methods of Saint Petersburg State University Research Park for obtaining the analytical data. Пристатейные ссылки: Hiesinger, K., Dar’in, D., Proschak, E., Krasavin, M., Spirocyclic Scaffolds in Medicinal Chemistry (2021) J. Med. Chem., 64, pp. 150-183; Ritchie, T.J., Macdonald, S.J., The impact of aromatic ring count on compound developability - are too many aromatic rings a liability in drug design? 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Lett., 17, pp. 5610-5613; Synofzik, J., Dar’in, D., Novikov, M.S., Kantin, G., Bakulina, O., Krasavin, M., alpha-Acyl-alpha-diazoacetates in Transition-Metal-Free beta-Lactam Synthesis (2019) J. Org. Chem., 84, pp. 12101-12110; Krasavin, M., Synofzik, J., Bakulina, O., Dar’in, D., Kantin, G., Dialkyl Diazomalonates in Transition-Metal-Free, Thermally Promoted, Diastereoselective Wolff β-Lactam Synthesis (2020) Synlett, 31, pp. 1273-1276; Golubev, A.A., Smetanin, I.A., Agafonova, A.V., Rostovskii, N.V., Khlebnikov, A.F., Starova, G.L., Novikov, M.S., [2 + 1 + 1] Assembly of spiro beta-lactams by Rh(II)-catalyzed reaction of diazocarbonyl compounds with azirines/isoxazoles (2019) Org. Biomol. 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Chem., 84, pp. 4534-4542; Eremeyeva, M., Zhukovsky, D., Dar’in, D., Krasavin, M., The Use of α-Diazo-γ-butyrolactams in the Büchner-Curtius-Schlotterbeck Reaction of Cyclic Ketones Opens New Entry to Spirocyclic Pyrrolidones (2020) Synlett, 31, pp. 982-986; Dar’in, D., Kantin, G., Bakulina, O., Inyutina, A., Chupakhin, E., Krasavin, M., Spirocyclizations Involving Oxonium Ylides Derived from Cyclic alpha-Diazocarbonyl Compounds: An Entry into 6-Oxa-2-azaspiro[4.5]decane Scaffold (2020) J. Org. Chem., 85, pp. 15586-15599; Dar’in, D., Kantin, G., Chupakhin, E., Sharoyko, V., Krasavin, M., Natural-Like Spirocyclic Δα,β-Butenolides Obtained from Diazo Homophthalimides (2021) Chem. - Eur. J., 27, pp. 8221-8227; Lowe, G., Ridley, D.D., Synthesis of β-lactams by photolytic Wolff rearrangement (1973) J. Chem. Soc., Perkin Trans. 1, pp. 2024-2029; Lowe, G., Yeung, H.W., Synthesis of a β-lactam related to the cephalosporins (1973) J. Chem. 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PY - 2024/2/16

Y1 - 2024/2/16

N2 - Herein, we report the study of the thermally promoted reaction of 3-diazotetramic acids with imines as a rapid route to a novel spiro heterocyclic scaffold, spiro bis-β-lactams (2,6-diazaspiro[3.3]heptane-1,5-diones). The transformation proceeds via metal-free microwave-assisted Wolff rearrangement of the diazo reagent followed by Staudinger [2+2] cycloaddition of the heterocyclic ketenes with Shiff bases. This methodology enables the preparation of diastereomerically pure spiro bis-β-lactams in high yields and provides an avenue for exploring new versions of the privileged β-lactam core for drug design. © 2024 American Chemical Society

AB - Herein, we report the study of the thermally promoted reaction of 3-diazotetramic acids with imines as a rapid route to a novel spiro heterocyclic scaffold, spiro bis-β-lactams (2,6-diazaspiro[3.3]heptane-1,5-diones). The transformation proceeds via metal-free microwave-assisted Wolff rearrangement of the diazo reagent followed by Staudinger [2+2] cycloaddition of the heterocyclic ketenes with Shiff bases. This methodology enables the preparation of diastereomerically pure spiro bis-β-lactams in high yields and provides an avenue for exploring new versions of the privileged β-lactam core for drug design. © 2024 American Chemical Society

KW - Amides

KW - Diazo reagents

KW - Drug Design

KW - Higher yield

KW - Metal free

KW - Microwave-assisted

KW - Shiff basis

KW - Wolff rearrangement

KW - [2 + 2] cycloaddition

KW - Scaffolds

UR - https://www.mendeley.com/catalogue/301a76f7-0a7a-30ee-b473-3484306be737/

U2 - 10.1021/acs.joc.3c02494

DO - 10.1021/acs.joc.3c02494

M3 - статья

VL - 89

SP - 3585

EP - 3589

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 5

ER -