Synthesis of Aryl Triolborates via Nickel-Catalyzed Borylation of Aryl Halides with 5-(tert-Butyldimethylsiloxymethyl)-5-methyl-1,3,2-dioxaborinane

Abstract

The nickel-catalyzed borylation of aryl halides with 5-(tert-butyldimethylsiloxymethyl)-5-methyl-1,3,2-dioxaborinane, prepared in situ, was achieved. The mild reaction conditions allowed common functional groups in the aryl halides to be tolerated. The products of this borylation are potential precursors of aryl triolborates.

Key words

carbon-boron bond formation - nickel catalysis - cross-coupling - aryl halides - hydroboranes

References

• 1a Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
• 1b Kotha S. Lahiri K. Kashinath D. Tetrahedron  2002,  58:  9633 
• 1c Martin R. Buchwald SL. Acc. Chem. Res.  2008,  41:  1461 
• 1d Darses S. Genet JP. Chem. Rev.  2008,  108:  288 
• 2a Yamamoto Y. Takizawa M. Yu XQ. Miyaura N. Angew. Chem. Int. Ed.  2008,  47:  928 
• 2b Yu XQ. Yamamoto Y. Miyaura N. Chem.-Asian J.  2008,  3:  1517 
• 2c Yu XQ. Yamamoto Y. Miyaura N. Synlett  2009,  994 
• 2d Yamamoto Y. Takizawa M. Yu X.-Q. Miyaura N. Heterocycles  2010,  81:  359 
• 2e Yu XQ. Shirai T. Yamamoto Y. Miyaura N. Chem.-Asian J.  2011,  3:  932 
• 3 Hall DG. In Boronic Acids   Hall DG. Wiley-VCH; Weinheim: 2005.  p.1 
• 4a Ishiyama T. Miyaura N. In Boronic Acids   Hall DG. Wiley-VCH; Weinheim: 2005.  p.101 
• 4b Merino P. Tejero T. Angew. Chem. Int. Ed.  2010,  49:  7164 
• 5a Murata M. Watanabe S. Masuda Y. J. Org. Chem.  1997,  62:  6458 
• 5b Murata M. Oyama T. Watanabe S. Masuda Y. J. Org. Chem.  2000,  65:  164 
• 6a Baudoin O. Guénard D. Guéritte F. J. Org. Chem.  2000,  65:  9268 
• 6b Broutin P.-E. Čerña I. Campaniello M. Leroux F. Colobert F. Org. Lett.  2004,  6:  4419 
• 6c Murata M. Sambommatsu T. Watanabe S. Masuda Y. Synlett  2006,  1867 
• 6d Billingsley KL. Buchwald SL. J. Org. Chem.  2008,  73:  5589 
• 7a Morgan AB. Jurs JL. Tour JM. J. Appl. Polym. Sci.  2000,  76:  1257 
• 7b Rosen BM. Huang C. Percec V. Org. Lett.  2008,  10:  2597 
• 8 Zhu W. Ma D. Org. Lett.  2006,  8:  261 
• 9 Quite recently, Yamamoto et al. reported on transesterification of pinacol arylboronic esters with 1,1,1-tris(hydroxymethyl)ethane. They developed a one-pot procedure for the synthesis of aryl triolborates from aryl halides through palladium-catalyzed borylation with pinacolborane, see: Li G.-Q. Kiyomura S. Yamamoto Y. Miyaura N. Chem. Lett.  2011,  40:  702 
• 11a Wilson DA. Wilson CJ. Rosen BM. Percec V. Org. Lett.  2008,  10:  4879 
• 11b Moldoveanu C. Wilson DA. Wilson CJ. Corcoran P. Rosen BM. Percec V. Org. Lett.  2009,  11:  4974 
• 11c Leowanawat P. Resmerita AM. Moldoveanu C. Liu C. Zhang N. Wilson DA. Hoang LM. Rosen BM. Percec V. J. Org. Chem.  2010,  75:  7822 
• 11d Moldoveanu C. Wilson DA. Wilson CJ. Leowanawat P. Resmerita AM. Liu C. Rosen BM. Percec V. J. Org. Chem.  2010,  75:  5438 
• 11e Wilson DA. Wilson CJ. Moldoveanu C. Resmerita AM. Corcoran P. Hoang LM. Rosen BM. Percec V. J. Am. Chem. Soc.  2010,  132:  1800 
• 12 Murata M. Sambommatsu T. Oda T. Watanabe S. Masuda Y. Heterocycles  2010,  80:  213 
• 13 Cunico RF. Bedell L. J. Org. Chem.  1980,  45:  4797 
• 14 Corey EJ. Venkateswarlu A. J. Am. Chem. Soc.  1972,  94:  6190 
• 15 Van Hecke GR. Horrocks WD. Inorg. Chem.  1966,  5:  1968 
• 16 McDougal PG. Rico JG. Oh YI. Condon BD.
  J. Org. Chem.  1986,  51:  3388 

10

Our attempts to isolate 5-(hydroxymethyl)-5-methyl-1,3,2-dioxaborinane also failed. Furthermore, the use of 1,1,1-tris(hydroxymethyl)ethane instead of 1 for the one-pot nickel-catalyzed borylation was lacking in reactivity and reproducibility (0-50% yield).