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Fernández, E.: 2020 Science of Synthesis, 2019/6: Advances in Organoboron Chemistry towards Organic Synthesis DOI: 10.1055/sos-SD-230-00232
Advances in Organoboron Chemistry towards Organic Synthesis

13 Boron “Ate” Complexes for Asymmetric Synthesis

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Editor: Fernández, E.

Authors: Aggarwal, V. K.; Ahmed, E.-A. M. A. ; Aiken, S. G.; Bateman, J. M.; Boldrini, C.; Bose, S. K. ; Carbó, J. J. ; Cho, H. Y.; Clark, T. B. ; Fernández, E.; Fu, Y. ; Geetharani, K. ; Gong, T.-J. ; Ito, H. ; Kitanosono, T.; Kobayashi, S.; Kubota, K. ; Maseras, F. ; Ohmiya, H. ; Pineschi, M.; Ping, Y.; Sawamura, M. ; Wang, J. ; Wang, Y.-F.; Wu, C.; Xu, L. ; Yoshida, H. ; Zhang, F.-L.

Title: Advances in Organoboron Chemistry towards Organic Synthesis

Print ISBN: 9783132429710; Online ISBN: 9783132429758; Book DOI: 10.1055/b-006-164898

2020 © 2020 Georg Thieme Verlag KG
Georg Thieme Verlag KG, Stuttgart

Subjects: Organic Chemistry;Chemical Reactions, Catalysis;Organometallic Chemistry;Laboratory Techniques, Stoichiometry

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Parent publication

Title: Science of Synthesis

DOI: 10.1055/b-00000101

Series Editors: Fürstner (Editor-in-Chief), A.; Carreira, E. M.; Faul, M.; Kobayashi, S.; Koch, G.; Molander, G. A.; Nevado, C.; Trost, B. M.; You, S.-L.

Type: Multivolume Edition

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Abstract

Addition of a nucleophile to a boronic ester results in the generation of a tetravalent boronate “ate” complex. If there is a leaving group stationed on the carbon atom α to the boron atom, the boronate complex can undergo stereospecific 1,2-migration with simultaneous expulsion of the leaving group to form a homologated boronic ester. The enantioselectivity of the process is dictated by either incorporating a chiral substituent into the boronic ester component (substrate control), or by forming a boronate complex through the addition of an enantioenriched carbenoid species to a boronic ester (reagent control). Activation of a boronic ester with organolithium reagents generates a nucleophilic boronate complex that acts as a chiral organometallic-type reagent, reacting with a wide range of electrophiles with inversion of stereochemistry. This chapter discusses methodology available for the enantioselective homologation of boronic esters using both substrate- and reagent-controlled strategies, and the development of boronate complexes as chiral nucleophiles.

Key words

Matteson reaction - substrate control - reagent control - homologation of boronic esters - asymmetric deprotonation - lithiation–borylation - 1,2-migration - 1,2-metalate rearrangement - stereospecific - assembly-line synthesis - contiguous stereocenters - chiral organometallic reagents
 
  • 1 D. S. Matteson,, K. M. Sadhu,, R. Ray,, P. K. Jesthi,, M. L. Peterson,, D. Majumdar,, D. J. S. Tsai,, G. D. Hurst,, E. Erdik,. J. Organomet. Chem.. 1985; 281: 15
    Google Scholar
  • 2 E. J. Corey,, D. Barnes-Seeman,, T. W. Lee,. Tetrahedron: Asymmetry. 1997; 8: 3711
    Google Scholar
  • 5 D. S. Matteson,, E. Erdik,. Organometallics. 1983; 2: 1083
    Google Scholar
  • 6 D. S. Matteson,, K. M. Sadhu,, M. L. Peterson,. J. Am. Chem. Soc.. 1986; 108: 810
    Google Scholar
  • 7 D. S. Matteson,, A. A. Kandil,. Tetrahedron Lett.. 1986; 27: 3831
    Google Scholar
  • 8 W. C. Hiscox,, D. S. Matteson,. J. Org. Chem.. 1996; 61: 8315
    Google Scholar
  • 9 P. B. Tripathy,, D. S. Matteson,. Synthesis. 1990; 200
    Google Scholar
  • 10 J. Gorges,, U. Kazmaier,. Org. Lett.. 2018; 20: 2033
    Google Scholar
  • 11 H. C. Brown,, S. M. Singh,. Organometallics. 1986; 5: 994
    Google Scholar
  • 12 D. Hoppe,, T. Hense,. Angew. Chem. Int. Ed. Engl.. 1997; 36: 2282
    Google Scholar
  • 13 P. Beak,, B. G. McKinnie,. J. Am. Chem. Soc.. 1977; 99: 5213
    Google Scholar
  • 14 D. Hoppe,, F. Hintze,, P. Tebben,. Angew. Chem. Int. Ed. Engl.. 1990; 29: 1422
    Google Scholar
  • 15 E. Beckmann,, V. Desai,, D. Hoppe,. Synlett. 2004; 2275
    Google Scholar
  • 16 J. L. Stymiest,, G. Dutheuil,, A. Mahmood,, V. K. Aggarwal,. Angew. Chem. Int. Ed.. 2007; 46: 7491
    Google Scholar
  • 17 R. C. Mykura,, S. Veth,, A. Varela,, L. Dewis,, J. J. Farndon,, E. L. Myers,, V. K. Aggarwal,. J. Am. Chem. Soc.. 2018; 140: 14677
    Google Scholar
  • 18 R. Larouche-Gauthier,, C. J. Fletcher,, I. Couto,, V. K. Aggarwal,. Chem. Commun. (Cambridge). 2011; 47: 12592
    Google Scholar
  • 19 D. Leonori,, V. K. Aggarwal,. Acc. Chem. Res.. 2014; 47: 3174
    Google Scholar
  • 20 A. P. Pulis,, D. J. Blair,, E. Torres,, V. K. Aggarwal,. J. Am. Chem. Soc.. 2013; 135: 16054
    Google Scholar
  • 21 A. Varela,, L. K. B. Garve,, D. Leonori,, V. K. Aggarwal,. Angew. Chem. Int. Ed.. 2017; 56: 2127
    Google Scholar
  • 22 R. Rasappan,, V. K. Aggarwal,. Nature Chem.. 2014; 6: 810
    Google Scholar
  • 23 J. L. Stymiest,, V. Bagutski,, R. M. French,, V. K. Aggarwal,. Nature (London). 2008; 456: 778
    Google Scholar
  • 24 V. Bagutski,, R. M. French,, V. K. Aggarwal,. Angew. Chem. Int. Ed.. 2010; 49: 5142
    Google Scholar
  • 25 C. G. Watson,, V. K. Aggarwal,. Org. Lett.. 2013; 15: 1346
    Google Scholar
  • 26 S. Roesner,, J. M. Casatejada,, T. G. Elford,, R. P. Sonawane,, V. K. Aggarwal,. Org. Lett.. 2011; 13: 5740
    Google Scholar
  • 27 K. R. Fandrick,, N. D. Patel,, J. A. Mulder,, J. Gao,, M. Konrad,, E. Archer,, F. G. Buono,, A. Duran,, R. Schmid,, J. Daeubler,, D. R. Fandrick,, S. Ma,, N. Grinberg,, H. Lee,, C. A. Busacca,, J. J. Song,, N. K. Yee,, C. H. Senanayake,. Org. Lett.. 2014; 16: 4360
    Google Scholar
  • 28 K. R. Fandrick,, J. A. Mulder,, N. D. Patel,, J. Gao,, M. Konrad,, E. Archer,, F. G. Buono,, A. Duran,, R. Schmid,, J. Daeubler,, J.-N. Desrosiers,, X. Zeng,, S. Rodriguez,, S. Ma,, B. Qu,, Z. Li,, D. R. Fandrick,, N. Grinberg,, H. Lee,, T. Bosanac,, H. Takahashi,, Z. Chen,, A. Bartolozzi,, P. Nemoto,, C. A. Busacca,, J. J. Song,, N. K. Yee,, P. E. Mahaney,, C. H. Senanayake,. J. Org. Chem.. 2015; 80: 1651
    Google Scholar
  • 29 D. J. Blair,, S. Zhong,, M. J. Hesse,, N. Zabaleta,, E. L. Myers,, V. K. Aggarwal,. Chem. Commun. (Cambridge). 2016; 52: 5289
    Google Scholar
  • 30 T. Krämer,, J.-R. Schwark,, D. Hoppe,. Tetrahedron Lett.. 1989; 30: 7037
    Google Scholar
  • 31 O. Zschage,, J.-R. Schwark,, D. Hoppe,. Angew. Chem. Int. Ed. Engl.. 1990; 29: 296
    Google Scholar
  • 32 A. P. Pulis,, V. K. Aggarwal,. J. Am. Chem. Soc.. 2012; 134: 7570
    Google Scholar
  • 33 B. M. Partridge,, L. Chausset-Boissarie,, M. Burns,, A. P. Pulis,, V. K. Aggarwal,. Angew. Chem. Int. Ed.. 2012; 51: 11795
    Google Scholar
  • 34 S. Dreller,, M. Dyrbusch,, D. Hoppe,. Synlett. 1991; 397
    Google Scholar
  • 35 P. Beak,, L. G. Carter,. J. Org. Chem.. 1981; 46: 2363
    Google Scholar
  • 36 D. Hoppe,, F. Marr,, M. Brüggemann,, Organolithiums in Enantioselective Synthesis. D. M. Hodgson,. Springer; London 2003
    Google Scholar
  • 37 D. J. Blair,, C. J. Fletcher,, K. M. P. Wheelhouse,, V. K. Aggarwal,. Angew. Chem. Int. Ed.. 2014; 53: 5552
    Google Scholar
  • 38 D. J. Blair,. 2015
  • 39 S. Roesner,, D. J. Blair,, V. K. Aggarwal,. Chem. Sci.. 2015; 6: 3718
    Google Scholar
  • 40 C. G. Watson,, A. Balanta,, T. G. Elford,, S. Essafi,, J. N. Harvey,, V. K. Aggarwal,. J. Am. Chem. Soc.. 2014; 136: 17370
    Google Scholar
  • 41 C. G. Watson,. 2014
  • 42 M. J. Dearden,, C. R. Frikin,, J.-P. R. Hermet,, P. OʼBrien,. J. Am. Chem. Soc.. 2002; 124: 11870
    Google Scholar
  • 43 M. Burns,, S. Essafi,, J. R. Bame,, S. P. Bull,, M. P. Webster,, S. Balieu,, J. W. Dale,, C. P. Butts,, J. N. Harvey,, V. K. Aggarwal,. Nature (London). 2014; 513: 183
    Google Scholar
  • 44 S. Balieu,, G. E. Hallett,, M. Burns,, T. Bootwicha,, J. Studley,, V. K. Aggarwal,. J. Am. Chem. Soc.. 2015; 137: 4398
    Google Scholar
  • 45 T. Bootwicha,, J. M. Feilner,, E. L. Myers,, V. K. Aggarwal,. Nature Chem.. 2017; 9: 896
    Google Scholar
  • 46 T. H. Chan,, P. Pellon,. J. Am. Chem. Soc.. 1989; 111: 8737
    Google Scholar
  • 47 G. R. Jones,, Y. Landais,. Tetrahedron. 1996; 52: 7599
    Google Scholar
  • 48 M. Chen,, W. R. Roush,. J. Am. Chem. Soc.. 2012; 134: 3925
    Google Scholar
  • 49 A. Fawcett,, D. Nitsch,, M. Ali,, J. M. Bateman,, E. L. Myers,, V. K. Aggarwal,. Angew. Chem. Int. Ed.. 2016; 55: 14663
    Google Scholar
  • 50 L. T. Kliman,, S. N. Mlynarski,, J. P. Morken,. J. Am. Chem. Soc.. 2009; 131: 13210
    Google Scholar
  • 51 J. R. Coombs,, F. Haeffner,, L. T. Kliman,, J. P. Morken,. J. Am. Chem. Soc.. 2013; 135: 11222
    Google Scholar
  • 52 K. Toribatake,, H. Nishiyama,. Angew. Chem. Int. Ed.. 2013; 52: 11011
    Google Scholar
  • 53 M. B. Boxer,, M. Akakura,, H. Yamamoto,. J. Am. Chem. Soc.. 2008; 130: 1580
    Google Scholar
  • 54 H. Y. Cho,, Z. Yu,, J. P. Morken,. Org. Lett.. 2011; 13: 5267
    Google Scholar
  • 55 D. J. Blair,, D. Tanini,, J. M. Bateman,, H. K. Scott,, E. L. Myers,, V. K. Aggarwal,. Chem. Sci.. 2017; 8: 2898
    Google Scholar
  • 56 D. S. Matteson,, J. Lu,. Tetrahedron: Asymmetry. 1998; 9: 2423
    Google Scholar
  • 57 K. Arnold,, A. S. Batsanov,, B. Davies,, C. Grosjean,, T. Schütz,, A. Whiting,, K. Zawatzky,. Chem. Commun. (Cambridge). 2008; 3879
    Google Scholar
  • 58 E. Vedrenne,, O. A. Wallner,, M. Vitale,, F. Schmidt,, V. K. Aggarwal,. Org. Lett.. 2009; 11: 165
    Google Scholar
  • 59 V. Capriati,, S. Florio,, R. Luisi,, A. Salomone,. Org. Lett.. 2002; 4: 2445
    Google Scholar
  • 60 F. Schmidt,, F. Keller,, E. Vedrenne,, V. K. Aggarwal,. Angew. Chem. Int. Ed.. 2009; 48: 1149
    Google Scholar
  • 61 D. M. Hodgson,, P. G. Humphreys,, S. M. Miles,, C. A. J. Brierley,, J. G. Ward,. J. Org. Chem.. 2007; 72: 10009
    Google Scholar
  • 62 D. M. Hodgson,, P. G. Humphreys,, Z. Xu,, J. G. Ward,. Angew. Chem. Int. Ed.. 2007; 46: 2245
    Google Scholar
  • 63 V. Capriati,, S. Florio,, R. Luisi,, B. Musio,. Org. Lett.. 2005; 7: 3749
    Google Scholar
  • 64 G. Casoni,, E. L. Myers,, V. K. Aggarwal,. Synthesis. 2016; 48: 3241
    Google Scholar
  • 65 I. Coldham,, J. J. Patel,, S. Raimbault,, D. T. E. Whittaker,, H. Adams,, G. Y. Fang,, V. K. Aggarwal,. Org. Lett.. 2008; 10: 141
    Google Scholar
  • 66 R. W. Hoffmann,, P. G. Nell,, R. Leo,, K. Harms,. Chem.–Eur. J.. 2000; 6: 3359
    Google Scholar
  • 67 V. Schulze,, P. G. Nell,, A. Burton,, R. W. Hoffmann,. J. Org. Chem.. 2003; 68: 4546
    Google Scholar
  • 68 A. Boudier,, P. Knochel,. Tetrahedron Lett.. 1999; 40: 687
    Google Scholar
  • 69 E. Hupe,, M. I. Calaza,, P. Knochel,. J. Organomet. Chem.. 2003; 680: 136
    Google Scholar
  • 70 E. Hupe,, M. I. Calaza,, P. Knochel,. Chem.–Eur. J.. 2003; 9: 2789
    Google Scholar
  • 71 T. Thaler,, B. Haag,, A. Gavryushin,, K. Schober,, E. Hartmann,, R. M. Gschwind,, H. Zipse,, P. Mayer,, P. Knochel,. Nature Chem.. 2010; 2: 125
    Google Scholar
  • 72 R. Larouche-Gauthier,, T. G. Elford,, V. K. Aggarwal,. J. Am. Chem. Soc.. 2011; 133: 16794
    Google Scholar
  • 73 C. Sandford,, R. Rasappan,, V. K. Aggarwal,. J. Am. Chem. Soc.. 2015; 137: 10100
    Google Scholar
  • 74 C. García-Ruiz,, J. L.-Y. Chen,, C. Sandford,, K. Feeney,, P. Lorenzo,, G. Berionni,, H. Mayr,, V. K. Aggarwal,. J. Am. Chem. Soc.. 2017; 139: 15324
    Google Scholar