Standard

Spirocyclizations Involving Oxonium Ylides Derived from Cyclic α-Diazocarbonyl Compounds : An Entry into 6-Oxa-2-azaspiro[4.5]decane Scaffold. / Dar'in, Dmitry; Kantin, Grigory; Bakulina, Olga; Inyutina, Anna; Chupakhin, Evgeny; Krasavin, Mikhail.

In: Journal of Organic Chemistry, Vol. 85, No. 23, 23.11.2020, p. 15586–15599.

Research output: Contribution to journal › Article › peer-review

Harvard

Dar'in, D, Kantin, G, Bakulina, O, Inyutina, A, Chupakhin, E & Krasavin, M 2020, 'Spirocyclizations Involving Oxonium Ylides Derived from Cyclic α-Diazocarbonyl Compounds: An Entry into 6-Oxa-2-azaspiro[4.5]decane Scaffold', Journal of Organic Chemistry, vol. 85, no. 23, pp. 15586–15599. https://doi.org/10.1021/acs.joc.0c02356

APA

Dar'in, D., Kantin, G., Bakulina, O., Inyutina, A., Chupakhin, E., & Krasavin, M. (2020). Spirocyclizations Involving Oxonium Ylides Derived from Cyclic α-Diazocarbonyl Compounds: An Entry into 6-Oxa-2-azaspiro[4.5]decane Scaffold. Journal of Organic Chemistry, 85(23), 15586–15599. https://doi.org/10.1021/acs.joc.0c02356

Vancouver

Dar'in D, Kantin G, Bakulina O, Inyutina A, Chupakhin E, Krasavin M. Spirocyclizations Involving Oxonium Ylides Derived from Cyclic α-Diazocarbonyl Compounds: An Entry into 6-Oxa-2-azaspiro[4.5]decane Scaffold. Journal of Organic Chemistry. 2020 Nov 23;85(23):15586–15599. https://doi.org/10.1021/acs.joc.0c02356

Author

Dar'in, Dmitry ; Kantin, Grigory ; Bakulina, Olga ; Inyutina, Anna ; Chupakhin, Evgeny ; Krasavin, Mikhail. / Spirocyclizations Involving Oxonium Ylides Derived from Cyclic α-Diazocarbonyl Compounds : An Entry into 6-Oxa-2-azaspiro[4.5]decane Scaffold. In: Journal of Organic Chemistry. 2020 ; Vol. 85, No. 23. pp. 15586–15599.

BibTeX

@article{e14d5efbefdf449b8f556122190838c5,
title = "Spirocyclizations Involving Oxonium Ylides Derived from Cyclic α-Diazocarbonyl Compounds: An Entry into 6-Oxa-2-azaspiro[4.5]decane Scaffold",
abstract = "New types of cyclic diazo compounds capable of Rh(II)-catalyzed spirocyclizations with tetrahydrofuran have been discovered. The formation of the spirocyclic framework is thought to proceed via the formation of Rh(II) carbene species followed by interaction with the Lewis basic oxygen atom of tetrahydrofuran to give oxonium ylide species. The latter evolves predominantly via the Stevens type rearrangement leading to an [n + 1] ring expansion of the tetrahydrofuran moiety, which results in the formation of a medicinally relevant 6-oxa-2-azaspiro[4.5]decane scaffold. The spirocyclization process was often observed in competition with mechanistically distinct C-H insertion into a tetrahydrofuran molecule. This competing process gave compounds based on the 3-(tetrahydrofur-2-yl)pyrrolidine scaffold, which are also relevant from the medicinal chemistry standpoint. These findings enrich the available arsenal of metal-catalyzed spirocyclization methods based on the use of cyclic diazo compounds. ",
author = "Dmitry Dar'in and Grigory Kantin and Olga Bakulina and Anna Inyutina and Evgeny Chupakhin and Mikhail Krasavin",
note = "Funding Information: This research was supported by the Russian Science Foundation (project grant 20-13-00024). We thank the Research Center for Magnetic Resonance, the Center for Chemical Analysis and Materials Research and the Center for X-ray Diffraction Methods of Saint Petersburg State University Research Park for obtaining the analytical data. Publisher Copyright: {\textcopyright} 2020 American Chemical Society. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.",
year = "2020",
month = nov,
day = "23",
doi = "10.1021/acs.joc.0c02356",
language = "English",
volume = "85",
pages = "15586–15599",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "23",

}

RIS

TY - JOUR

T1 - Spirocyclizations Involving Oxonium Ylides Derived from Cyclic α-Diazocarbonyl Compounds

T2 - An Entry into 6-Oxa-2-azaspiro[4.5]decane Scaffold

AU - Dar'in, Dmitry

AU - Kantin, Grigory

AU - Bakulina, Olga

AU - Inyutina, Anna

AU - Chupakhin, Evgeny

AU - Krasavin, Mikhail

N1 - Funding Information: This research was supported by the Russian Science Foundation (project grant 20-13-00024). We thank the Research Center for Magnetic Resonance, the Center for Chemical Analysis and Materials Research and the Center for X-ray Diffraction Methods of Saint Petersburg State University Research Park for obtaining the analytical data. Publisher Copyright: © 2020 American Chemical Society. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/11/23

Y1 - 2020/11/23

N2 - New types of cyclic diazo compounds capable of Rh(II)-catalyzed spirocyclizations with tetrahydrofuran have been discovered. The formation of the spirocyclic framework is thought to proceed via the formation of Rh(II) carbene species followed by interaction with the Lewis basic oxygen atom of tetrahydrofuran to give oxonium ylide species. The latter evolves predominantly via the Stevens type rearrangement leading to an [n + 1] ring expansion of the tetrahydrofuran moiety, which results in the formation of a medicinally relevant 6-oxa-2-azaspiro[4.5]decane scaffold. The spirocyclization process was often observed in competition with mechanistically distinct C-H insertion into a tetrahydrofuran molecule. This competing process gave compounds based on the 3-(tetrahydrofur-2-yl)pyrrolidine scaffold, which are also relevant from the medicinal chemistry standpoint. These findings enrich the available arsenal of metal-catalyzed spirocyclization methods based on the use of cyclic diazo compounds.

AB - New types of cyclic diazo compounds capable of Rh(II)-catalyzed spirocyclizations with tetrahydrofuran have been discovered. The formation of the spirocyclic framework is thought to proceed via the formation of Rh(II) carbene species followed by interaction with the Lewis basic oxygen atom of tetrahydrofuran to give oxonium ylide species. The latter evolves predominantly via the Stevens type rearrangement leading to an [n + 1] ring expansion of the tetrahydrofuran moiety, which results in the formation of a medicinally relevant 6-oxa-2-azaspiro[4.5]decane scaffold. The spirocyclization process was often observed in competition with mechanistically distinct C-H insertion into a tetrahydrofuran molecule. This competing process gave compounds based on the 3-(tetrahydrofur-2-yl)pyrrolidine scaffold, which are also relevant from the medicinal chemistry standpoint. These findings enrich the available arsenal of metal-catalyzed spirocyclization methods based on the use of cyclic diazo compounds.

UR - http://www.scopus.com/inward/record.url?scp=85097890667&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/9b3b47db-b860-364e-bb98-85ebef284aae/

U2 - 10.1021/acs.joc.0c02356

DO - 10.1021/acs.joc.0c02356

M3 - Article

AN - SCOPUS:85097890667

VL - 85

SP - 15586

EP - 15599

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 23

ER -

ID: 72053104