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DOI: 10.1055/s-0040-1719882
Significant Broadening of the Substrate Scope for the Hydrated Imidazoline Ring Expansion (HIRE) via the Use of Lithium Hexamethyldisilazide
This research was supported by the Russian Science Foundation (Grant no. 19-75-30008).
Abstract
Substrates that are insufficiently activated towards the hydrated imidazoline ring expansion (HIRE) process have been previously found to deliver exclusively the products of aminoalkyl side-chain ring expansion. Attempted reversal of the process by thermal activation towards HIRE failed. We have found that for such problematic substrates the HIRE-type ring expansion can be effectively achieved by applying lithium hexamethyldisilazide (LHMDS) in toluene. LHMDS is thought to promote intramolecular transamidation, which leads to ring-expanded 10- and 11-membered heterocyclic products in modest to good yields. The process significantly broadens the substrate scope amenable to the HIRE strategy.
Key words
[1,4]diazepinones - [1,4]ox(thi)azepinones - fused imidazolinium moiety - hydrated imidazoline ring expansion - aminoalkyl sidechain incorporation - lithium hexamethyldisilazide - facilitated intramolecular transamidationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1719882.
- Supporting Information
Publication History
Received: 26 November 2021
Accepted after revision: 16 December 2021
Article published online:
10 February 2022
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References
- 1 Zhao C, Ye Z, Ma Z.-x, Wildmaan SA, Blaszczyk SA, Hu L, Guizei IA, Tang W. Nat. Commun. 2019; 10: 4015
- 2a Yet L. Chem. Rev. 2000; 100: 2963
- 2b Molander GA. Acc. Chem. Res. 1998; 31: 603
- 2c Illuminati G, Mandolini L. Acc. Chem. Res. 1981; 14: 95
- 2d Galli C, Mandolini L. Eur. J. Org. Chem. 2000; 3117
- 2e Sharma A, Appukkuttan P, Van der Eycken E. Chem. Commun. 2012; 48: 1623
- 3a Shiina I. Chem. Rev. 2007; 107: 239
- 3b Yudin AK. Chem. Sci. 2015; 6: 30
- 3c Baud LG, Manning MA, Arkless HL, Stephens TC, Unsworth WP. Chem. Eur. J. 2017; 23: 2225
- 4a Reutskaya E, Sapegin A, Peintner S, Erdélyi M, Krasavin M. J. Org. Chem. 2021; 86: 5778
- 4b Grintsevich S, Sapegin A, Reutskaya E, Peintner S, Erdélyi M, Krasavin M. Eur. J. Org. Chem. 2020; 5664
- 4c Sapegin A, Osipyan A, Krasavin M. Org. Biomol. Chem. 2017; 15: 2906
- 4d Osipyan A, Sapegin A, Novikov A, Krasavin M. J. Org. Chem. 2018; 83: 9707
- 4e Grintsevich S, Sapegin A, Reutskaya E, Krasavin M. Tetrahedron Lett. 2019; 60: 20
- 5 Grintsevich A, Sapegin A, Duszinska B, Bojarski AJ, Krasavin M. Synthesis 2022; 54: 658
- 6 Lavit K, Reutskaya E, Grintsevich S, Sapegin A, Krasavin M. Tetrahedron Lett. 2020; 61: 152423
- 7 Reutskaya E, Osipyan A, Sapegin A, Novikov A, Krasavin M. J. Org. Chem. 2019; 84: 1693
- 8 Li G, Szostak M. Nat. Commun. 2018; 9: 4165
- 9a Li G, Ma S, Szostak M. Synthesis 2020; 52: 2579
- 9b Li G, Ma S, Szostak M. Trends Chem. 2020; 2: 914
- 10 Tryniszewski M, Bujok R, Gańczarczyk R, Wróbel Z. Synthesis 2020; 52: 3086
- 11a Li G, Ji C.-L, Hong X, Szostak M. J. Am. Chem. Soc. 2019; 141: 11161
- 11b Raman M, Li G, Szostak M. J. Org. Chem. 2019; 84: 12091
- 12 Becerra-Figueroa L, Ojeda-Porras A, Gamba-Sanchez D. J. Org. Chem. 2014; 79: 4544
- 13 Eldred SE, Stone DA, Gellman SH, Stahl SS. J. Am. Chem. Soc. 2003; 125: 3422
- 14 Bon E, Bigg DC. H, Bertrand G. J. Org. Chem. 1994; 59: 4035
- 15 Nguyen TB, Sorres J, Tran MQ, Ermolenko L, Al-Mourabit A. Org. Lett. 2012; 14: 3202