Ring-Strain-Promoted Transformations of Bicyclo/Azabicyclo[1.1.0]butane-Derived Boronic Esters

doi:10.6023/cjoc202603021

Abstract

Bicyclo[1.1.0]butane- and azabicyclo[1.1.0]butane-derived boronic esters (BCB-Bpins) combine high ring strain with the versatile reactivity of organoboron groups, and their transformations are typically driven by strain release. This review summarizes recent advances in BCB-Bpin chemistry through three main pathways: ionic pathways, such as nucleophilic 1,2-shift in boronate complexes; radical approaches, including strain-release-driven additions to BCB-Bpins; and transition-metal-catalyzed stereoselective functionalizations, especially Pd- and Ir-catalyzed stereoselective and asymmetric difunctionalizations. Representative studies, mechanistic features, selectivity control, current challenges, and future opportunities are also discussed.

Key words: boronate complexes, ring-strain-promoted transformations, catalytic asymmetric transformations

Cite this article

Tian-Ge Dong, Chong-Lei Ji, De-Wei Gao. Ring-Strain-Promoted Transformations of Bicyclo/Azabicyclo[1.1.0]butane-Derived Boronic Esters[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202603021.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] (a) Wiberg, K. B. Angew. Chem. Int. Ed. 1986, 25, 312.
(b) Sella, A.; Basch, H.; Hoz, S. J. Am. Chem. Soc. 1996, 118, 416.
(c) Turkowska, J.; Durka, J.; Gryko, D. Chem. Commun. 2020, 56, 5718.
(d) Bellotti, P.; Glorius, F. J. Am. Chem. Soc. 2023, 145, 20716.
[2] (a) Wiberg, K. B.; Lampman, G. M.; Ciula, R. P.; Connir, D. S.; Schertler, P.; Lavanish, J. Tetrahedron 1965, 21, 2749.
(b) Kelly, C. B.; Milligan, J. A.; Tilley, L. J.; Sodano, T. M. Chem. Sci. 2022, 13, 11721.
(c) Pramanik, M. M. D.; Qian, H.; Xiao, W.-J.; Chen, J.-R. Org. Chem. Front. 2020, 7, 2531.
(d) Tsien, J.; Hu, C.; Merchant, R. R.; Qin, T. Nat. Rev. Chem. 2024, 8, 605.
(e) Zhan, X.; He, H.-X.; Peng, Q.; Feng, J.-J. Synthesis 2024, 56, 3829.
(f) Cuadros, S.; Paut, J.; Anselmi, E.; Dagousset, G.; Magnier, E.; Dell'Amico, L. Angew. Chem. Int. Ed. 2024, 63, e202317333.
(g) Zhou, X.; Hu, Y.; Huang, Y.; Xiong, Y. Chem. Commun. 2025, 61, 23.
(h) Yang, X.-C.; Wang, J.-J.; Xiao, Y.; Feng, J.-J. Angew. Chem. Int. Ed. 2025, 64, e202505803.
(i) Xiao, Y.; Tang, L.; Yang, X.-C.; Wang, N.-Y.; Zhang, J.; Deng, W.-P.; Feng, J.-J. CCS Chem. 2025, 7, 1903.
(j) Koo, Y.; Jeong, J.; Hong, S. ACS Catal. 2025, 15, 8078.
[3] Golfmann M.; Walker, J. C. L. Commun. Chem.2023, 6, 9.
[4] (a) Wrobleski, M. L.; Reichard, G. A.; Paliwal, S.; Shah, S.; Tsui, H.-C.; Duffy, R. A.; Lachowicz, J. E.; Morgan, C. A.; Varty, G. B.; Shih, N.-Y. Bioorg. Med. Chem. Lett. 2006, 16, 3859.
(b) Vitaku, E.; Smith, D. T.; Njardarson, J. T. J. Med. Chem. 2014, 57, 10257.
(c) Rice, K. D.; Aay, N.; Anand, N. K.; Blazey, C. M.; Bowles, O. J.; Bussenius, J.; Costanzo, S.; Curtis, J. K.; Defina, S. C.; Dubenko, L.; Engst, S.; Joshi, A. A.; Kennedy, A. R.; Kim, A. I.; Koltun, E. S.; Lougheed, J. C.; Manalo, J.-C. L.; Martini, J.-F.; Nuss, J. M.; Peto, C. J.; Tsang, T. H.; Yu, P.; Johnston, S. ACS Med. Chem. Lett. 2012, 3, 416.
(d) Oizumi, K.; Nishino, H.; Koike, H.; Sada, T.; Miyamoto, M.; Kimura, T. Jpn. J. Pharmacol. 1989, 51, 57.
(e) Tyler J. L.; Aggarwal, V. K. Chem. Eur. J. 2023, 29, e202300008.
[5] (a) Hall, D. G. Boronic acids: preparation and applications in organic synthesis, medicine and materials, 2nd ed.; Wiley-VCH: Weinheim, Germany, 2011.
(b) Matteson, D. S.; Ray, R. J. Am. Chem. Soc. 1980, 102, 7590.
(c) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
(d) Matteson, D. S. Tetrahedron 1998, 54, 10555.
(e) Trippier, P. C.; McGuigan, C. Med. Chem. Commun. 2010, 1, 183.
(f) Suzuki, A. Angew. Chem. Int. Ed. 2011, 50, 6722.
(g) Matteson, D. S. J. Org. Chem. 2013, 78, 10009.
(h) Lennox, A. J. J.; Lloyd-Jones, G. C. Chem. Soc. Rev. 2014, 43, 412.
(i) Leonori, D.; Aggarwal, V. K. Acc. Chem. Res. 2014, 47, 3174.
(j) Xu, L.; Zhang, S.; Li, P. Chem. Soc. Rev. 2015, 44, 8848.
(k) Brooks, W. L. A.; Sumerlin, B. S. Chem. Rev. 2016, 116, 1375.
(l) Diner, C.; Szabó, K. J. J. Am. Chem. Soc. 2017, 139, 2.
(m) Fyfe, J. W. B.; Watson, A. J. B. Chem 2017, 3, 31.
(n) Sandford, C.; Aggarwal, V. K. Chem. Commun. 2017, 53, 5481.
(o) Rygus, J. P. G.; Crudden, C. M. J. Am. Chem. Soc. 2017, 139, 18124.
(p) Kalita, S. J.; Cheng, F.; Huang, Y.-Y. Adv. Synth. Catal. 2020, 362, 2778.
(q) Yeung, K.; Mykura, R. C.; Aggarwal, V. K. Nat. Synth. 2022, 1, 117.
(r) Jiang, X.-M.; Liu, X.-R.; Chen, A.; Zou, X.-Z.; Ge, J.-F.; Gao. D.-W. Eur. J. Org. Chem. 2022, e202101463.
(s) Yu, I. F.; Wilson, J. W.; Hartwig, J. F. Chem. Rev. 2023, 123, 11619.
(t) Ji, C.-L.; Gao, D.-W. Chin. J. Org. Chem. 2024, 44, 1385 (in Chinese).
(吉崇磊, 高得伟, 有机化学, 2024, 44, 1385.)
(u) Zhao, J.-H.; Chen, A.; Zou, X.-Z.; Ji, C.-L.; Feng, H.; Gao, D.-W. Chin. J. Chem. 2024, 42, 3484.
[6] (a) Fawcett A.; Biberger T.; Aggarwal, V. K. Nat. Chem.2019, 11, 117.
(b) Fawcett A.; Murtaza A.; Gregson C. H. U.; Aggarwal, V. K. J. Am. Chem. Soc.2019, 141, 4573.
[7] Michalland J.; Casaretto N.; Zard, S. Z. Angew. Chem., Int. Ed.2022, 61, e202113333.
[8] Silvi M.; Aggarwal, A. K. J. Am. Chem. Soc.2019, 141, 9511.
[9] Bagutski V.; Ros A.; Aggarwal V. K. Tetrahedron2009, 65, 9956.
[10] (a) Sadhu K. M.; Matteson D. S. Organometallics1985, 4, 1687.
(b) Balieu S.; Hallett G. E.; Burns M.; Bootwicha T.; Studley J.; Aggarwal, V. K. J. Am. Chem. Soc.2015, 137, 4398.
[11] (a) Zweifel G.; Arzoumanian H.; Whitney, C. J. Am. Chem. Soc.1967, 89, 3652.
(b) Armstrong R. J.; Aggarwal V. K. Synthesis2017, 49, 3323.
[12] Lewis-Borrell L.; Sneha M.; Clark I. P.; Fasano V.; Noble A.; Aggarwal V. K.; Orr-Ewing, A. J. J. Am. Chem. Soc.2021, 143, 17191.
[13] (a) Antermite D.; Degennaro L.; Luisi, R. Org. Biomol. Chem.2017, 15, 34.
(b) Brandi A.; Cicchi S.; Cordero, F. M. Chem. Rev.2008, 108, 3988.
[14] Armstrong R. J.; Niwetmarin W.; Aggarwal, V. K. Org. Lett.2017, 19, 2762.
[15] Llaveria J.; Leonori D.; Aggarwal, V. K. J. Am. Chem. Soc.2015, 137, 10958.
[16] Bennett, S. H.; Fawcett, A.; Denton, E. H.; Biberger, T.; Fasano, V.; Winter, N.; Aggarwal, V. K.J. Am. Chem. Soc. 2020, 142, 16766.
[17] Guo L.; Noble A.; Aggarwal, V. K. Angew. Chem., Int. Ed.2021, 60, 212.
[18] (a) Bonet A.; Odachowski M.; Leonori D.; Essafi S.; Aggarwal, V. K. Nat. Chem.2014, 6, 584.
(b) Odachowski M.; Bonet A.; Essafi S.; Conti-Ramsden P.; Harvey J. N.; Leonori D.; Aggarwal, V. K. J. Am. Chem. Soc.2016, 138, 9521.
[19] Wang, Y.; Noble, A.; Myers, E. L.; Aggarwal, V. K.Angew. Chem., Int. Ed. 2016, 55, 4270.
[20] Mlynarski S. N.; Karns A. S.; Morken, J. P. J. Am. Chem. Soc.2012, 134, 16449.
[21] Shen, H.-C.; Popescu, M. V.; Wang, Z.-S.; de Lescure, L.; Noble, A.; Paton, R. S.; Aggarwal, V. K.J. Am. Chem. Soc. 2023, 145, 16508.
[22] (a) Zhang L.; Lovinger G. J.; Edelstein E. K.; Szymaniak A. A.; Chierchia M. P.; Morken J. P. Science2016, 351, 70.
(b) Namirembe S.; Morken, J. P. Chem. Soc. Rev. 2019, 48,3464.
(c) Wang, H.; Jing, C.; Noble, A.; Aggarwal, V. K.Angew. Chem., Int. Ed. 2020, 59, 16859.
[23] (a) Hartwig J. F.; Pouy, M. J. Top. Organomet. Chem.2011, 34, 169.
(b) Hartwig, J. F.; Stanley, L. M.Acc. Chem. Res. 2010, 43, 1461.
(c) Hethcox, J. C.; Shockley, S. E.; Stoltz, B. M. ACS Catal. 2016, 6, 6207., 2138.
[24] (a) Davis C. R.; Luvaga I. K.; Ready, J. M. J. Am. Chem. Soc.2021, 143, 4921.
(b) Davis C. R.; Fu Y.; Liu P.; Ready, J. M. J. Am. Chem. Soc.2022, 144, 16118.
(c) Ge J.-F.; Zou X.-Z.; Liu X.-R.; Ji C.-L.; Zhu X.-Y.; Gao, D.-W. Angew. Chem. Int. Ed.2023, 62, e202307447.
[25] Sun Y.-W.; Zhao J.-H.; Yan X.-Y.; Ji C.-L.; Feng H.; Gao D.-W. Nat. Commun.2024, 15, 10810.
[26] (a) Carmona, J. A.; Rodríguez-Franco, C.; Fernández, R.; Hornillos, V.; Lassaletta, J. M. Chem. Soc. Rev. 2021, 50, 2968.
(b) Ros, A.; Estepa, B.; Ramírez-López, P.; Álvarez, E.; Fernández, R.; Lassaletta, J. M. J. Am. Chem. Soc. 2013, 135, 15730.
(c) Bhat, V.; Wang, S.; Stoltz, B. M.; Virgil, S. C. J. Am. Chem. Soc. 2013, 135, 16829.
(d) Han, S.-J.; Bhat, V.; Stoltz, B. M.; Virgil, S. C. Adv. Synth. Catal. 2019, 361, 441.
(e) Ramírez-López, P.; Ros, A.; Romero-Arenas, A.; Iglesias-Sigüenza, J.; Fernández, R.; Lassaletta, J. M. J. Am. Chem. Soc. 2016, 138, 12053.
(f) Ramírez-López, P.; Ros, A.; Estepa, B.; Fernández, R.; Fiser, B.; Gómez-Bengoa, E.; Lassaletta, J. M. ACS Catal. 2016, 6, 3955.
(g) Carmona, J. A.; Hornillos, V.; Ramírez-López, P.; Ros, A.; Iglesias-Sigüenza, J.; Gómez-Bengoa, E.; Fernández, R.; Lassaletta, J. M. J. Am. Chem. Soc. 2018, 140, 11067.
(h) Zou X.-Z.; Sun Y.-W.; Gao D.-W. Sci. Adv.2025, 11, eadz8755.
[27] Zhu, X.-Y.; Ji, C.-L.; Dong, T.-G.; Gao, D.-W.Nat. Commun. 2026, 17, 1941.
[28] (a) Trost B. M.; McEachern E. J.; Toste, F. D. J. Am. Chem. Soc.1998, 120, 12702.
(b) Khan A.; Khan S.; Khan I.; Zhao C.; Mao Y.; Chen Y.; Zhang, Y. J. J. Am. Chem. Soc.2017, 139, 10733.
[29] (a) Jiang X.-M.; Ji C.-L.; Ge J.-F.; Zhao J.-H.; Zhu X.-Y.; Gao, D.-W. Angew. Chem. Int. Ed.2024, 63, e202318441.
(b) Ji C.-L.; Gao D.-W. Trends Chem.2024, 6, 211.
[30] Yamamoto Y.; Fujikawa, R; Umemoto T.; Miyaura N. Tetrahedron2004, 60, 10695.
[31] Scholl M.; Ding S.; Lee C. W.; Grubbs, R. H. Org. Lett.1999, 1, 953.

环张力促进的双环/氮杂双环[1.1.0]丁烷硼酸酯的转化