13 Boron “Ate” Complexes for Asymmetric Synthesis

S. G. Aiken; J. M. Bateman; V. K. Aggarwal

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.

Schlüsselwörter

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 Matteson DS, Sadhu KM, Ray R, Jesthi PK, Peterson ML, Majumdar D, Tsai DJS, Hurst GD, Erdik E. J. Organomet. Chem. 1985; 281: 15

• 2 Corey EJ, Barnes-Seeman D, Lee TW. Tetrahedron: Asymmetry 1997; 8: 3711

• 3 Matteson DS. Sci. Synth. 2005; 6: 585

• 4 Midland MM. J. Org. Chem. 1998; 63: 914

• 5 Matteson DS, Erdik E. Organometallics 1983; 2: 1083

• 6 Matteson DS, Sadhu KM, Peterson ML. J. Am. Chem. Soc. 1986; 108: 810

• 7 Matteson DS, Kandil AA. Tetrahedron Lett. 1986; 27: 3831

• 8 Hiscox WC, Matteson DS. J. Org. Chem. 1996; 61: 8315

• 9 Tripathy PB, Matteson DS. Synthesis 1990; 200

• 10 Gorges J, Kazmaier U. Org. Lett. 2018; 20: 2033

• 11 Brown HC, Singh SM. Organometallics 1986; 5: 994

• 12 Hoppe D, Hense T. Angew. Chem. Int. Ed. Engl. 1997; 36: 2282

• 13 Beak P, McKinnie BG. J. Am. Chem. Soc. 1977; 99: 5213

• 14 Hoppe D, Hintze F, Tebben P. Angew. Chem. Int. Ed. Engl. 1990; 29: 1422

• 15 Beckmann E, Desai V, Hoppe D. Synlett 2004; 2275

• 16 Stymiest JL, Dutheuil G, Mahmood A, Aggarwal VK. Angew. Chem. Int. Ed. 2007; 46: 7491

• 17 Mykura RC, Veth S, Varela A, Dewis L, Farndon JJ, Myers EL, Aggarwal VK. J. Am. Chem. Soc. 2018; 140: 14677

• 18 Larouche-Gauthier R, Fletcher CJ, Couto I, Aggarwal VK. Chem. Commun. (Cambridge) 2011; 47: 12592

• 19 Leonori D, Aggarwal VK. Acc. Chem. Res. 2014; 47: 3174

• 20 Pulis AP, Blair DJ, Torres E, Aggarwal VK. J. Am. Chem. Soc. 2013; 135: 16054

• 21 Varela A, Garve LKB, Leonori D, Aggarwal VK. Angew. Chem. Int. Ed. 2017; 56: 2127

• 22 Rasappan R, Aggarwal VK. Nature Chem. 2014; 6: 810

• 23 Stymiest JL, Bagutski V, French RM, Aggarwal VK. Nature (London) 2008; 456: 778

• 24 Bagutski V, French RM, Aggarwal VK. Angew. Chem. Int. Ed. 2010; 49: 5142

• 25 Watson CG, Aggarwal VK. Org. Lett. 2013; 15: 1346

• 26 Roesner S, Casatejada JM, Elford TG, Sonawane RP, Aggarwal VK. Org. Lett. 2011; 13: 5740

• 27 Fandrick KR, Patel ND, Mulder JA, Gao J, Konrad M, Archer E, Buono FG, Duran A, Schmid R, Daeubler J, Fandrick DR, Ma S, Grinberg N, Lee H, Busacca CA, Song JJ, Yee NK, Senanayake CH. Org. Lett. 2014; 16: 4360

• 28 Fandrick KR, Mulder JA, Patel ND, Gao J, Konrad M, Archer E, Buono FG, Duran A, Schmid R, Daeubler J, Desrosiers J.-N, Zeng X, Rodriguez S, Ma S, Qu B, Li Z, Fandrick DR, Grinberg N, Lee H, Bosanac T, Takahashi H, Chen Z, Bartolozzi A, Nemoto P, Busacca CA, Song JJ, Yee NK, Mahaney PE, Senanayake CH. J. Org. Chem. 2015; 80: 1651

• 29 Blair DJ, Zhong S, Hesse MJ, Zabaleta N, Myers EL, Aggarwal VK. Chem. Commun. (Cambridge) 2016; 52: 5289

• 30 Krämer T, Schwark J.-R, Hoppe D. Tetrahedron Lett. 1989; 30: 7037

• 31 Zschage O, Schwark J.-R, Hoppe D. Angew. Chem. Int. Ed. Engl. 1990; 29: 296

• 32 Pulis AP, Aggarwal VK. J. Am. Chem. Soc. 2012; 134: 7570

• 33 Partridge BM, Chausset-Boissarie L, Burns M, Pulis AP, Aggarwal VK. Angew. Chem. Int. Ed. 2012; 51: 11795

• 34 Dreller S, Dyrbusch M, Hoppe D. Synlett 1991; 397

• 35 Beak P, Carter LG. J. Org. Chem. 1981; 46: 2363

• 36 Hoppe D, Marr F, Brüggemann M, In: Organolithiums in Enantioselective Synthesis Hodgson DM. Springer London 2003; 73

• 37 Blair DJ, Fletcher CJ, Wheelhouse KMP, Aggarwal VK. Angew. Chem. Int. Ed. 2014; 53: 5552

• 38 Blair DJ Ph.D. Dissertation, University of Bristol 2015

• 39 Roesner S, Blair DJ, Aggarwal VK. Chem. Sci. 2015; 6: 3718

• 40 Watson CG, Balanta A, Elford TG, Essafi S, Harvey JN, Aggarwal VK. J. Am. Chem. Soc. 2014; 136: 17370

• 41 Watson CG Ph.D. Dissertation, University of Bristol 2014

• 42 Dearden MJ, Frikin CR, Hermet J.-PR, OʼBrien P. J. Am. Chem. Soc. 2002; 124: 11870

• 43 Burns M, Essafi S, Bame JR, Bull SP, Webster MP, Balieu S, Dale JW, Butts CP, Harvey JN, Aggarwal VK. Nature (London) 2014; 513: 183

• 44 Balieu S, Hallett GE, Burns M, Bootwicha T, Studley J, Aggarwal VK. J. Am. Chem. Soc. 2015; 137: 4398

• 45 Bootwicha T, Feilner JM, Myers EL, Aggarwal VK. Nature Chem. 2017; 9: 896

• 46 Chan TH, Pellon P. J. Am. Chem. Soc. 1989; 111: 8737

• 47 Jones GR, Landais Y. Tetrahedron 1996; 52: 7599

• 48 Chen M, Roush WR. J. Am. Chem. Soc. 2012; 134: 3925

• 49 Fawcett A, Nitsch D, Ali M, Bateman JM, Myers EL, Aggarwal VK. Angew. Chem. Int. Ed. 2016; 55: 14663

• 50 Kliman LT, Mlynarski SN, Morken JP. J. Am. Chem. Soc. 2009; 131: 13210

• 51 Coombs JR, Haeffner F, Kliman LT, Morken JP. J. Am. Chem. Soc. 2013; 135: 11222

• 52 Toribatake K, Nishiyama H. Angew. Chem. Int. Ed. 2013; 52: 11011

• 53 Boxer MB, Akakura M, Yamamoto H. J. Am. Chem. Soc. 2008; 130: 1580

• 54 Cho HY, Yu Z, Morken JP. Org. Lett. 2011; 13: 5267

• 55 Blair DJ, Tanini D, Bateman JM, Scott HK, Myers EL, Aggarwal VK. Chem. Sci. 2017; 8: 2898

• 56 Matteson DS, Lu J. Tetrahedron: Asymmetry 1998; 9: 2423

• 57 Arnold K, Batsanov AS, Davies B, Grosjean C, Schütz T, Whiting A, Zawatzky K. Chem. Commun. (Cambridge) 2008; 3879

• 58 Vedrenne E, Wallner OA, Vitale M, Schmidt F, Aggarwal VK. Org. Lett. 2009; 11: 165

• 59 Capriati V, Florio S, Luisi R, Salomone A. Org. Lett. 2002; 4: 2445

• 60 Schmidt F, Keller F, Vedrenne E, Aggarwal VK. Angew. Chem. Int. Ed. 2009; 48: 1149

• 61 Hodgson DM, Humphreys PG, Miles SM, Brierley CAJ, Ward JG. J. Org. Chem. 2007; 72: 10009

• 62 Hodgson DM, Humphreys PG, Xu Z, Ward JG. Angew. Chem. Int. Ed. 2007; 46: 2245

• 63 Capriati V, Florio S, Luisi R, Musio B. Org. Lett. 2005; 7: 3749

• 64 Casoni G, Myers EL, Aggarwal VK. Synthesis 2016; 48: 3241

• 65 Coldham I, Patel JJ, Raimbault S, Whittaker DTE, Adams H, Fang GY, Aggarwal VK. Org. Lett. 2008; 10: 141

• 66 Hoffmann RW, Nell PG, Leo R, Harms K. Chem.–Eur. J. 2000; 6: 3359

• 67 Schulze V, Nell PG, Burton A, Hoffmann RW. J. Org. Chem. 2003; 68: 4546

• 68 Boudier A, Knochel P. Tetrahedron Lett. 1999; 40: 687

• 69 Hupe E, Calaza MI, Knochel P. J. Organomet. Chem. 2003; 680: 136

• 70 Hupe E, Calaza MI, Knochel P. Chem.–Eur. J. 2003; 9: 2789

• 71 Thaler T, Haag B, Gavryushin A, Schober K, Hartmann E, Gschwind RM, Zipse H, Mayer P, Knochel P. Nature Chem. 2010; 2: 125

• 72 Larouche-Gauthier R, Elford TG, Aggarwal VK. J. Am. Chem. Soc. 2011; 133: 16794

• 73 Sandford C, Rasappan R, Aggarwal VK. J. Am. Chem. Soc. 2015; 137: 10100

• 74 García-Ruiz C, Chen JL.-Y, Sandford C, Feeney K, Lorenzo P, Berionni G, Mayr H, Aggarwal VK. J. Am. Chem. Soc. 2017; 139: 15324