One-Pot Preparation of Stable Organoboronate Reagents for the Functionalization of Unsaturated Four- and Five-Membered Carbo­- and Heterocycles

^‡ These authors contributed equally to this work.

Published as part of the Special Topic Modern Coupling Approaches and their Strategic Applications in Synthesis

Abstract

Combining a facile preparation of organoboronates with their remarkable stability and functional group tolerance allows for the straightforward synthesis of four- and five-membered carbo- and hetero­cycles. While most strategies rely on the ex situ preparation of boronic acids as isolated intermediates, we demonstrate that in situ transmetalation of sensitive organometallics with boron alkoxides can lead to great stabilization of such species at room temperature. A considerable extension of the library of unsaturated strained structures is achieved through these sequences, expanding the potential applicability of such unusual building blocks.

Key words

cyclobutenes - cyclopentenes - azetines - organoboronates - one-pot sequences

• References

• 1a Miyaura N. Suzuki A. J. Chem. Soc., Chem. Commun. 1979; 866
• 1b Miyaura N. Yamada K. Suzuki A. Tetrahedron Lett. 1979; 36: 3437
• 1c Suzuki A. Angew. Chem. Int. Ed. 2011; 50: 6722
• 2a Lennox AJ. J. Lloyd-Jones GC. Chem. Soc. Rev. 2014; 43: 412
• 2b Maluenda I. Navarro O. Molecules 2015; 20: 7528
• 2c Han F.-S. Chem. Soc. Rev. 2013; 42: 5270
• 3a Synthesis and Application of Organoboron Compounds. In Topics in Organometallic Chemistry. Vol. 49. Fernández E. Whiting A. Springer; Cham: 2015
• 3b Brown HC. Cole TC. Organometallics 1983; 2: 1316
• 3c Boronic Acids: Preparation, Applications in Organic Synthesis and Medicine. Hall DG. Wiley-VCH; Weinheim: 2005
• 4a Trippier PC. McGuigan C. MedChemComm 2010; 1: 183
• 4b Draganov A. Wang D. Wang B. In Atypical Elements in Drug Design . In Topics in Medicinal Chemistry . Vol. 17. Schwarz J. Springer; Cham: 2014
• 5 Brooks WL. A. Sumerlin BS. Chem. Rev. 2016; 116: 1375
• 6 Bull SD. Davidson MG. van den Elsen JM. H. Fossey JS. Jenkins AT. A. Jiang Y.-B. Kubo Y. Marken F. Sakurai K. Zhao J. James TD. Acc. Chem. Res. 2013; 46: 312
• 7 Nicolaou KC. Bulger PG. Sarlah D. Angew. Chem. Int. Ed. 2005; 44: 4442
• 8a Billingsley KL. Buchwald SL. Angew. Chem. Int. Ed. 2008; 47: 4695
• 8b Oberli MA. Buchwald SL. Org. Lett. 2012; 14: 4606
• 9a Yamamoto Y. Takizawa M. Yu X.-Q. Miyaura N. Angew. Chem. Int. Ed. 2008; 47: 928
• 9b Yamamoto Y. Ikizakura K. Ito H. Miyaura N. Molecules 2013; 18: 430
• 10 Cammidge AN. Goddard VH. M. Gopee H. Harrison NL. Hughes DL. Schubert CJ. Sutton BM. Watts GL. Whitehead AJ. Org. Lett. 2006; 8: 4072
• 11 Haag BA. Sämann C. Jana A. Knochel P. Angew. Chem. Int. Ed. 2011; 50: 7290
• 12a Boardman LD. Bagheri V. Sawada H. Negishi E.-i. J. Am. Chem. Soc. 1984; 106: 6105
• 12b Liu F. Negishi E.-i. Tetrahedron Lett. 1997; 38: 1149
• 13a Eisold M. Didier D. Angew. Chem. Int. Ed. 2015; 54: 15884
• 13b Eisold M. Kiefl GM. Didier D. Org. Lett. 2016; 18: 3022
• 13c Eisold M. Baumann AN. Kiefl GM. Emmerling ST. Didier D. Chem. Eur. J. 2017; 23: 1634
• 13d Baumann AN. Eisold M. Didier D. Org. Lett. 2017; 19: 2114
• 13e Eisold M. Didier D. Org. Lett. 2017; 19: 4046
• 14 Hodgson DM. Pearson CI. Kazmi M. Org. Lett. 2014; 16: 856
• 15 Baumann AN. Eisold M. Music A. Haas G. Kiw YM. Didier D. Org. Lett. 2017; 19: 5681
• 16 CCDC 1825251 (3a), CCDC 1826225 (4g) and CCDC 1825250 (7a) contain the supplementary crystallographic data for this manuscript. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures. See the Supporting Information for details.
• 17 Negishi E.-i. Sawada H. Tour JM. Wei Y. J. Org. Chem. 1988; 53: 915
• 18 Li W. Nelson DP. Jensen MS. Hoerrner RS. Cai D. Larsen RD. Reider PJ. J. Org. Chem. 2002; 67: 5394