Accessing Azetidines through Magnesium-Mediated Nitrogen Group Transfer from Iminoiodinane to Donor-Acceptor Cyclopropanes
This article relates to:
-
Marvin Parasram
- Volume 137Issue 23Angewandte Chemie
- First Published online: April 14, 2025
Dr. Ajay H. Bansode
Department of Chemistry, New York University, New York, New York, 10003 United States
Search for more papers by this authorLifeng Yin
Department of Chemistry, New York University, New York, New York, 10003 United States
Search for more papers by this authorNing Deng
Department of Chemistry, New York University, New York, New York, 10003 United States
Ning Deng and Mahmoud Afrasi contributed to this work equally.
Search for more papers by this authorMahmoud Afrasi
Department of Chemistry, New York University, New York, New York, 10003 United States
Ning Deng and Mahmoud Afrasi contributed to this work equally.
Search for more papers by this authorYiyi Zhu
Department of Teaching and Learning, New York University, New York, New York, 10003 United States
Search for more papers by this authorCorresponding Author
Prof. Dr. Marvin Parasram
Department of Chemistry, New York University, New York, New York, 10003 United States
Search for more papers by this authorDr. Ajay H. Bansode
Department of Chemistry, New York University, New York, New York, 10003 United States
Search for more papers by this authorLifeng Yin
Department of Chemistry, New York University, New York, New York, 10003 United States
Search for more papers by this authorNing Deng
Department of Chemistry, New York University, New York, New York, 10003 United States
Ning Deng and Mahmoud Afrasi contributed to this work equally.
Search for more papers by this authorMahmoud Afrasi
Department of Chemistry, New York University, New York, New York, 10003 United States
Ning Deng and Mahmoud Afrasi contributed to this work equally.
Search for more papers by this authorYiyi Zhu
Department of Teaching and Learning, New York University, New York, New York, 10003 United States
Search for more papers by this authorCorresponding Author
Prof. Dr. Marvin Parasram
Department of Chemistry, New York University, New York, New York, 10003 United States
Search for more papers by this authorAbstract
Herein, we report a Lewis acid-mediated ring expansion of donor-acceptor cyclopropanes (DACs) to substituted azetidines via nucleophilic nitrogen group transfer from readily accessible iminoiodinane. This protocol operates under mild, transition-metal-free conditions, and showcases excellent chemoselectivity, along with broad functional group tolerance. We report for the first time that challenging alkyl donor-acceptor cyclopropanes can undergo ring expansion leading to aliphatic azetidines without relying on external oxidants or precious transition-metal catalysts. Mechanistically, the coordination of a magnesium (Mg)-Lewis acid to the DAC promotes nucleophilic ring opening with a putative Mg-amide species generated from the iminoiodinane under the reaction conditions to furnish the azetidine products.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
Supporting Information
As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.
| Filename | Description |
|---|---|
| ange202420485-sup-0001-misc_information.pdf10.2 MB | Supporting Information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1M. W. Holladay, J. T. Wasicak, N.-H. Lin, Y. He, K. B. Ryther, A. W. Bannon, M. J. Buckley, D. J. Kim, M. W. Decker, D. J. Anderson, J. Med. Chem. 1998, 41, 407–412.
- 2J. I. Kobayashi, J. F. Cheng, M. Ishibashi, M. R. Wälchli, S. Yamamura, Y. Ohizumi, J. Chem. Soc. Perkin Trans. 1 1991, 5, 1135–1137.
- 3J. D. Rodgers, S. Shepard, T. P. Maduskuie, H. Wang, N. Falahatpisheh, M. Rafalski, A. G. Arvanitis, L. Sorace, R. K. Jalluri, J. S. Fridman, K. Vaddi, US Patent 0135461 A1, June 14, 2007.
- 4D. R. Parmar, J. Y. Soni, R. Guduru, R. H. Rayani, R. V. Kusurkar, A. G. Vala, Arch. Pharm. 2021, 354, e2100062.
- 5I. O. Feskov, A. V. Chernykh, Y. O. Kuchkovska, C. G. Daniliuc, I. S. Kondratov, O. O. Grygorenko, J. Org. Chem. 2019, 84, 1363–1371.
- 6J. Basinger, B. Bookser, M. Chen, A. Hudson, J. Na, J. Renick, V. Santora, US Patent 0334846 A1, November 23, 2017.
- 7
- 7aG. S. Singh, M. D'hooghe, N. De Kimpe, in Comprehensive Heterocyclic Chemistry III, ed. C. V. Stevens, Elsevier, Oxford, 3rd edn, 2008, 2, 1–110;
10.1016/B978-008044992-0.00201-7 Google Scholar
- 7bF. Couty, Sci. Synth. 2009, 40a, 773–816;
- 7cG. Rousseau, S. Robin, in Modern Heterocyclic Chemistry, ed. J. Alzerez-Builla, J. J. Vaquero, J. Barluenga, Wiley-VCH, Weinheim, 1st edn. 2011, 1, 163–268;
10.1002/9783527637737.ch3 Google Scholar
- 7dS. Liu, N. Shao, F.-Z. Li, X.-C. Yang, M.-C. Wang, Org. Biomol. Chem. 2017, 15, 9465–9474.
- 8
- 8aL. Reisman, E. A. Rowe, E. M. Jackson, C. Thomas, T. Simone, P. A. Rupar, J. Am. Chem. Soc. 2018, 140, 15626–15630;
- 8bF. Couty, O. David, F. Durrat, G. Evano, S. Lakhdar, J. Marrot, M. Vargas-Sanchez, Eur. J. Org. Chem. 2006, 3479–3490.
- 9H. Mughal, M. Szostak, Org. Biomol. Chem. 2021, 19, 3274–3286.
- 10G. S. Singh, in Advances in heterocyclic chemistry, Elsevier, 2020, 130, 1–74.
10.1016/bs.aihch.2019.10.001 Google Scholar
- 11
- 11aE. R. Wearing, Y.-C. Yeh, G. G. Terrones, S. G. Parikh, I. Kevlishvili, H. J. Kulik, C. S. Schindler, Science 2024, 384, 1468–1476;
- 11bR. Dasi, A. Villinger, M. Brasholz, Org. Lett. 2022, 24, 8041–8046;
- 11cM. R. Becker, E. R. Wearing, C. S. Schindler, Nat. Chem. 2020, 12, 898–905.
- 12N. Kern, A.-S. Felten, J.-M. Weibel, P. Pale, A. Blanc, Org. Lett. 2014, 16, 6104–6107.
- 13
- 13aS. Malik, U. K. Nadir, P. S. Pandey, Synth. Commun. 2010, 40, 1631–1638;
- 13bS. Stankovic, S. Catak, M. D'hooghe, H. Goossens, A. K. Tehrani, P. Bogaert, M. Waroquier, V. V. Speybroeck, N. De Kimpe, J. Org. Chem. 2011, 76, 2157–2167.
- 14Y. Ji, L. Wojtas, J. M. Lopchuk, Arkivoc 2018, 195–214.
- 15
- 15aA. Jacob, P. G. Jones, D. B. Werz, Org. Lett. 2020, 22, 8720–8724;
- 15bM. Bao, M. P. Doyle, Org. Lett. 2023, 25, 3029–3033;
- 15cM. Bao, K. Lopez, R. Gurung, H. Arman, M. P. Doyle, ACS Catal. 2023, 13, 1621–1629.
- 16
- 16aG. Mloston, M. Celeda, M. Kowalczyk, G. A. Oliver, D. B. Werz, Eur. J. Org. Chem. 2024, e202400831;
- 16bE. M. Budynina, K. L. Ivanov, I. D. Sorokin, M. Y. Melnikov, Synthesis 2017, 49, 3035–3068;
- 16cS. J. Webster, L. B. Balázs, F. W. Goetzke, V. Stojalnikova, K. Liu, K. E. Christensen, H. W. Mackenzie, S. P. Fletcher, J. Am. Chem. Soc. 2024, 146, 24708–24715.
- 17Selected examples for donor-acceptor cyclopropane ring-opening strategies:
- 17aS. Chakrabarty, I. Chatterjee, B. Wibbeling, C. G. Daniliuc, A. Studer, Angew. Chem. Int. Ed. 2014, 53, 5964–5968;
- 17bJ. Wallbaum, L. K. Garve, P. G. Jones, D. B. Werz, Org. Lett. 2017, 19, 98–101;
- 17cS. Deswal, A. Guin, A. T. Biju, Org. Lett. 2023, 25, 1643–1648;
- 17dA. Guin, S. Deswal, A. T. Biju, J. Org. Chem. 2022, 87, 6504–6513.
- 18
- 18aA. U. Augustin, J. L. Merz, P. G. Jones, G. Mloston, D. B. Werz, Org. Lett. 2019, 21, 9405–9409;
- 18bA. U. Augustin, M. Sensse, P. G. Jones, D. B. Werz, Angew. Chem. Int. Ed. 2017, 56, 14293–14296.
- 19
- 19aT. F. Schneider, J. Kaschel, D. B. Werz, Angew. Chem. Int. Ed. 2014, 53, 5504–5523;
- 19bH.-U. Reissig, R. Zimmer, Chem. Rev. 2003, 103, 1151–1196;
- 19cD. B. Werz, A. T. Biju, Angew. Chem. Int. Ed. 2020, 59, 3385–3398.
- 20H. H. Zhang, Y. C. Luo, H. P. Wang, W. Chen, P. F. Xu, Org. Lett. 2014, 16, 4896–4899.
- 21A. Ghosh, S. Mandal, P. K. Chattaraj, P. Banerjee, Org. Lett. 2016, 18, 4940–4943.
- 22J. Q. Han, H. H. Zhang, P. F. Xu, Y. C. Luo, Org. Lett. 2016, 18, 5212–5215.
- 23Y. Ju, R. S. Varma, J. Org. Chem. 2006, 71, 135–141.
- 24J. K. Mitchell, W. A. Hussain, A. H. Bansode, R. M. O'Connor, M. Parasram, J. Am. Chem. Soc. 2024, 146, 9499–9505.
- 25
- 25aY. Guo, C. Pei, C. Empel, S. Jana, R. M. Koenigs, ChemPhotoChem 2022, 6, e202100293;
- 25bY. Guo, C. Pei, S. Jana, R. M. Koenigs, ACS Catal. 2020, 11, 337–342.
- 26J. W. W. Chang, T. M. U. Ton, P. W. H. Chan, Chem. Rec. 2011, 11, 331–357.
- 27Y.-C. Wang, X.-J. Lai, K. Huang, S. Yadav, G. Qiu, L. Zhang, H. Zhou, Org. Chem. Front. 2021, 8, 1677–1693.
- 28D. B. Bagal, S.-W. Park, H.-J. Song, S. Chang, Chem. Commun. 2017, 53, 8798–8801.
- 29
- 29aD. A. Denisov, R. A. Novikov, K. V. Potapov, V. A. Korolev, E. V. Shulishov, Y. V. Tomilov, ChemistrySelect 2016, 1, 6374–6381;
- 29bK. V. Potapov, D. A. Denisov, V. V. Glushkova, R. A. Novikov, Y. V. Tomilov, J. Org. Chem. 2020, 85, 15562–15576;
- 29cO. A. Ivanova, V. A. Andronov, V. S. Vasin, A. N. Shumsky, V. B. Rybakov, L. G. Voskressensky, I. V. Trushkov, Org. Lett. 2018, 20, 7947–7952.
- 30A. Kreft, A. Lücht, J. Grunenberg, P. G. Jones, D. B. Werz, Angew. Chem. Int. Ed. 2019, 58, 1955–1959.
- 31
- 31aM. Shimizu, Sci. Synth. 2004, 7, 661–667;
- 31bR. Sanz, G. Vest, L. Despres, Synth. Commun. 1989, 19, 2909–2913;
- 31cL. Davin, A. Hernán-Gómez, C. McLaughlin, A. R. Kennedy, R. McLellan, E. Hevia, Dalton Trans. 2019, 48, 8122–8130;
- 31dR. Campbell, B. Conway, G. S. Fairweather, P. García-Álvarez, A. R. Kennedy, J. Klett, R. E. Mulvey, C. T. O′Hara, G. M. Robertson, Dalton Trans. 2010, 39, 511–519.
- 32S. Das, C. G. Daniliuc, A. Studer, Angew. Chem. Int. Ed. 2017, 56, 11554–11558.
- 33J. Guo, G. Hu, Z. Chen, Trans. Tianjin Univ. 2012, 18, 8–14.
- 34S. P. Fritz, J. F. Moya, M. G. Unthank, E. M. McGarrigle, V. K. Aggarwal, Synthesis 2012, 44, 1584–1590.
- 35D. E. Wise, E. S. Gogarnoiu, A. D. Duke, J. M. Paolillo, T. L. Vacala, W. A. Hussain, M. Parasram, J. Am. Chem. Soc. 2022, 144, 15437–15442.
- 36M. K. Ghorai, A. Kumar, K. Das, Org. Lett. 2007, 9, 5441–5444.
This is the
German version
of Angewandte Chemie.
Note for articles published since 1962:
Do not cite this version alone.
Take me to the International Edition version with citable page numbers, DOI, and citation export.
We apologize for the inconvenience.
