Synlett 2016; 27(07): 969-976
DOI: 10.1055/s-0035-1561248
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© Georg Thieme Verlag Stuttgart · New York

Selective Activation of Arylboronate or Aryne Reactivity as a Versatile Postfunctionalization Strategy

Johanna Larsson
a  OnTarget Chemistry, Virdings alle 32b, 75-450 Uppsala, Sweden
,
Emilien Demory
b  Department of Chemistry – BMC, Uppsala University, Box 576, 75-123 Uppsala, Sweden   URL: www.pilarskigroup.org   Email: lukasz.pilarski@kemi.uu.se
,
Karthik Devaraj
b  Department of Chemistry – BMC, Uppsala University, Box 576, 75-123 Uppsala, Sweden   URL: www.pilarskigroup.org   Email: lukasz.pilarski@kemi.uu.se
,
Carina Sollert
b  Department of Chemistry – BMC, Uppsala University, Box 576, 75-123 Uppsala, Sweden   URL: www.pilarskigroup.org   Email: lukasz.pilarski@kemi.uu.se
,
Lukasz T. Pilarski*
b  Department of Chemistry – BMC, Uppsala University, Box 576, 75-123 Uppsala, Sweden   URL: www.pilarskigroup.org   Email: lukasz.pilarski@kemi.uu.se
› Author Affiliations
Further Information

Publication History

Received: 03 December 2015

Accepted after revision: 21 December 2015

Publication Date:
20 January 2016 (eFirst)

Dedicated to the memory of Professor Richard F. Heck

Abstract

This review discusses the preparation and orthogonal reactivity of boryl ortho-silyl(hetero)aryl triflates as precursors for arynes. These triflates undergo a wide variety of selective reactions of either the boronate or aryne component. Activation of the boronate group affords diverse (hetero)aryne precursors, whereas aryne activation and capture gives previously difficult-to-access arylboronates, all starting from the same set of common starting materials. Thus, the boronate and aryne functionality can be used for their mutual postfunctionalization with unprecedented flexibility.

 
  • References

    • 1a Wenk HH, Winkler M, Sander W. Angew. Chem. Int. Ed. 2003; 42: 502
    • 1b Bhunia A, Yetra SR, Biju AT. Chem. Soc. Rev. 2012; 3140
    • 1c Wu C, Shi F. Asian J. Org. Chem. 2013; 2: 116
    • 1d Holden C, Greaney MF. Angew. Chem. Int. Ed. 2014; 53: 5746
    • 1e Yoshida H, Takaki K. Synlett 2012; 23: 1725
    • 1f Dubrovskiy AV, Markina NA, Larock RC. Org. Biomol. Chem. 2013; 11: 191
    • 1g Pérez D, Peña D, Guitián E. Eur. J. Org. Chem. 2013; 5981
    • 1h Yoshida S, Hosoya T. Chem. Lett. 2015; 44: 1450
    • 1i Miyabe H. Molecules 2015; 20: 12558
  • 2 Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials. Hall DG. Wiley-VCH; Weinheim: 2011
    • 3a Stoermer R, Kahlert B. Ber. Dtsch. Chem. Ges. 1902; 35: 1633
    • 3b Lüttringhaus A, Saaf G. Justus Liebigs Ann. Chem. 1930; 592: 250
  • 4 Wittig G. Naturwissenschaften 1942; 30: 696
    • 5a Roberts JD, Simmons HE, Carlsmith LA, Vaughan CW. J. Am. Chem. Soc. 1953; 75: 3290
    • 5b Roberts JD, Semenow DA, Simmons HE. Jr, Carlsmith LA. J. Am. Chem. Soc. 1956; 78: 601
    • 5c Pavliček N, Schuler B, Collazos S, Moll S, Pérez D, Guitián E, Meyer G, Peña D, Gross L. Nat. Chem. 2015; 7: 623
    • 6a Gampe CM, Carreira EM. Angew. Chem. Int. Ed. 2012; 51: 3766
    • 6b Tadross PM, Stoltz BM. Chem. Rev. 2012; 112: 3550
    • 6c Goetz AE, Shah TK, Garg NK. Chem. Commun. 2015; 51: 34
    • 7a Oliva-Madrid M.-J, Saura-Llamas I, Bautista D, Vicente J. Chem. Commun. 2013; 49: 7997
    • 7b Oliva-Madrid M.-J, García-López J.-A, Saura-Llamas I, Bautista D, Vicente J. Organometallics 2014; 33: 6420
  • 8 Wu D, Ge H, Liu SH, Yin J. RSC Adv. 2013; 3: 22727
  • 9 Cunico RF, Dexheimer EM. J. Organomet. Chem. 1973; 59: 153
  • 10 Himeshima Y, Sonoda T, Kobayashi H. Chem. Lett. 1983; 1211
    • 11a Ikawa T, Nishiyama T, Nosaki T, Takagi A, Akai S. Org. Lett. 2011; 13: 1730
    • 11b Kovács S, Csincsi AI, Nagy TZ, Boros S, Timári G, Novák Z. Org. Lett. 2012; 14: 2022
    • 11c Kitamura T, Yamane M, Inoue K, Todaka M, Fukatsu N, Meng Z, Fujiwara Y. J. Am. Chem. Soc. 1999; 121: 11674
    • 12a Ikawa T, Nishiyama T, Shigeta T, Mohri S, Morita S, Takayanagi S.-i, Terauchi Y, Morikawa Y, Takagi A, Ishikawa Y, Fujii S, Kita Y, Akai S. Angew. Chem. Int. Ed. 2011; 50: 5674
    • 12b Ikawa T, Urata H, Fukumoto Y, Sumii Y, Nishiyama T, Akai S. Chem. Eur. J. 2014; 20: 16228
    • 13a Picazo E, Houk KN, Garg NK. Tetrahedron Lett. 2015; 56: 3511
    • 13b Medina JM, Mackey JL, Garg NK, Houk KN. J. Am. Chem. Soc. 2014; 136: 15798
    • 13c Goetz AE, Garg NK. Nat. Chem. 2012; 5: 54
    • 13d Goetz AE, Bronner SM, Cisneros JD, Melamed JM, Paton RS, Houk KN, Garg NK. Angew. Chem. Int. Ed. 2012; 51: 2758
    • 13e Bronner SM, Mackey JL, Houk KN, Garg NK. J. Am. Chem. Soc. 2012; 134: 13966
    • 13f Bronner SM, Goetz AE, Garg NK. Synlett 2011; 2011: 2599
    • 13g Cheong P.-HY, Paton RS, Bronner SM, Im G.-YJ, Garg NK, Houk KN. J. Am. Chem. Soc. 2010; 132: 1267
  • 14 Im G.-YJ, Bronner SM, Goetz AE, Paton RS, Cheong P.-HY, Houk KN, Garg NK. J. Am. Chem. Soc. 2010; 132: 17933
  • 15 Tadross PM, Gilmore CD, Bugga P, Virgil SC, Stoltz BM. Org. Lett. 2010; 12: 1224
  • 16 Demory E, Devaraj K, Orthaber A, Gates PJ, Pilarski LT. Angew. Chem. Int. Ed. 2015; 54: 11765
    • 17a Noguchi H, Hojo K, Suginome M. J. Am. Chem. Soc. 2007; 129: 758
    • 17b Noguchi H, Shioda T, Chou C.-M, Suginome M. Org. Lett. 2008; 10: 377
    • 18a Gillis EP, Burke MD. J. Am. Chem. Soc. 2007; 129: 6716
    • 18b Gillis EP, Burke MD. Aldrichimica Acta 2009; 42: 17
  • 19 Wang C, Glorius F. Angew. Chem. Int. Ed. 2009; 48: 5240
  • 20 Xu L, Zhang S, Li P. Chem. Soc. Rev. 2015; 44: 8848
  • 21 Merritt EA, Olofsson B. Angew. Chem. Int. Ed. 2009; 48: 9052
  • 22 Ito M, Itani I, Toyoda Y, Morimoto K, Dohi T, Kita Y. Angew. Chem. Int. Ed. 2012; 51: 12555
    • 23a Xu L, Ding S, Li P. Angew. Chem. Int. Ed. 2014; 53: 1822
    • 23b Xu L, Li P. Chem. Commun. 2015; 51: 5656
    • 24a Fyfe JW. B, Seath CP, Watson AJ. B. Angew. Chem. Int. Ed. 2014; 53: 12077
    • 24b Fyfe JW. B, Valverde E, Seath CP, Kennedy AR, Redmond JM, Anderson NA, Watson AJ. B. Chem. Eur. J. 2015; 21: 8951
    • 24c Seath CP, Fyfe JW. B, Molloy JJ, Watson AJ. B. Angew. Chem. Int. Ed. 2015; 54: 9976
    • 24d Fyfe JW. B, Watson AJ. B. Synlett 2015; 26: 1139
  • 25 For a recent review of various boron reagents used in Suzuki–Miyaura coupling, see: Lennox AJ. J, Lloyd-Jones GC. Chem. Soc. Rev. 2014; 43: 412
    • 26a Heinrich AC. J, Thiedemann B, Gates PJ, Staubitz A. Org. Lett. 2013; 15: 4666
    • 26b Linshoeft J, Heinrich AC. J, Segler SA. W, Gates PJ, Staubitz A. Org. Lett. 2012; 14: 5644
  • 27 Ihara H, Suginome M. J. Am. Chem. Soc. 2009; 131: 7502
  • 28 Ihara H, Koyanagi M, Suginome M. Org. Lett. 2011; 13: 2662
  • 29 Qiu D, Mo F, Zheng Z, Zhang Y, Wang J. Org. Lett. 2010; 12: 5474
  • 30 Al-Zoubi RM, Hall DG. Org. Lett. 2010; 12: 2480
    • 31a Ikawa T, Takagi A, Kurita Y, Saito K, Azechi K, Egi M, Kakiguchi K, Kita Y, Akai S. Angew. Chem. Int. Ed. 2010; 49: 5563
    • 31b Ikawa T, Takagi A, Goto M, Aoyama Y, Ishikawa Y, Itoh Y, Fujii S, Tokiwa H, Akai S. J. Org. Chem. 2013; 78: 2965
    • 31c Takagi A, Ikawa T, Kurita Y, Saito K, Azechi K, Egi M, Itoh Y, Tokiwa H, Kita Y, Akai S. Tetrahedron 2013; 69: 4338
    • 31d Takagi A, Ikawa T, Saito K, Masuda S, Ito T, Akai S. Org. Biomol. Chem. 2013; 11: 8145
  • 32 Sollert C, Devaraj K, Orthaber A, Gates PJ, Pilarski LT. Chem. Eur. J. 2015; 21: 5380
    • 33a Iverson CN, Smith MR. J. Am. Chem. Soc. 1999; 121: 7696
    • 33b Chen H, Schlecht S, Semple TC, Hartwig JF. Science 2000; 287: 1995
    • 33c Cho J.-Y, Tse MK, Holmes D, Maleczka RE. Jr, Smith MR. III. Science 2002; 295: 305
    • 33d Ishiyama T, Takagi J, Hartwig JF, Miyaura N. Angew. Chem. Int. Ed. 2002; 41: 3056
    • 33e Ishiyama T, Takagi J, Ishida K, Miyaura N, Anastasi NR, Hartwig JF. J. Am. Chem. Soc. 2002; 124: 390

    • For selected reviews, see:
    • 33f Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
    • 33g Hartwig JF. Chem. Soc. Rev. 2011; 40: 1992
    • 33h Hartwig JF. Acc. Chem. Res. 2012; 45: 864
    • 34a Cho J.-Y, Iverson CN, Smith MR. J. Am. Chem. Soc. 2000; 122: 12868

    • To a first approximation, Ir-catalyzed C-H borylation is selective for the least sterically hindered Ar–H bonds in simple arenes. In reality, the regioselectivity of this process is a more complex topic and the subject of several detailed mechanistic studies. For examples, see:
    • 34b Vanchura BA. II, Preshlock SM, Roosen PC, Kallepalli VA, Staples RJ, Maleczka RE. Jr, Singleton DA, Smith MR. III. Chem. Commun. 2010; 46: 7724
    • 34c Larsen MA, Hartwig JF. J. Am. Chem. Soc. 2014; 136: 4287
    • 34d Sadler SA, Tajuddin H, Mkhalid IA. I, Batsanov AS, Albesa-Jove D, Cheung MS, Maxwell AC, Shukla L, Roberts B, Blakemore DC, Lin Z, Marder TB, Steel PG. Org. Biomol. Chem. 2014; 12: 7318
    • 34e Tajuddin H, Harrisson P, Bitterlich B, Collings JC, Sim N, Batsanov AS, Cheung MS, Kawamorita S, Maxwell AC, Shukla L, Morris J, Lin Z, Marder TB, Steel PG. Chem. Sci. 2012; 3: 3505
    • 34f Hurst TE, Macklin TK, Becker M, Hartmann E, Kügel W, Parisienne-La Salle J.-C, Batsanov AS, Marder TB, Snieckus V. Chem. Eur. J. 2010; 16: 8155
    • 34g Sadler SA, Hones AC, Roberts B, Blakemore D, Marder TB, Steel PG. J. Org. Chem. 2015; 80: 5308
  • 35 Jayasundara CR. K, Unold JM, Oppenheimer J, Smith MR. III, Maleczka RE. Jr. Org. Lett. 2014; 16: 6072
  • 36 Paul S, Chotana GA, Holmes D, Reichle RC, Maleczka RE. Jr, Smith MR. III. J. Am. Chem. Soc. 2006; 128: 15552
  • 37 Dyke AM, Hester AJ, Lloyd-Jones GC. Synthesis 2006; 4093
  • 38 Raminelli C, Liu Z, Larock RC. J. Org. Chem. 2006; 71: 4689
    • 39a Yoshida H, Shirakawa E, Honda Y, Hiyama T. Angew. Chem. Int. Ed. 2002; 41: 3247
    • 39b Saito N, Nakamura K.-i, Shibano S, Ide S, Minami M, Sato Y. Org. Lett. 2013; 15: 386
  • 40 Pilarski LT, Szabó KJ. Angew. Chem. Int. Ed. 2011; 50: 8230
    • 41a Alonso JM, Díaz-Álvarez AE, Criado A, Pérez D, Peña D, Guitián E. Angew. Chem. Int. Ed. 2012; 51: 173
    • 41b Schuler B, Collazos S, Gross L, Meyer G, Pérez D, Guitián E, Peña D. Angew. Chem. Int. Ed. 2014; 53: 9004
  • 42 Sun J, Perfetti MT, Santos WL. J. Org. Chem. 2011; 76: 3571
  • 43 Gillis EP, Burke MD. J. Am. Chem. Soc. 2008; 130: 14084
    • 44a Wright SW, Hageman DL, McClure LD. J. Org. Chem. 1994; 59: 6095
    • 44b PraveenGanesh N, Chavant PY. Eur. J. Org. Chem. 2008; 2008: 4690
  • 45 Molander GA, Ellis N. Acc. Chem. Res. 2007; 40: 275
  • 46 Lennox AJ. J, Lloyd-Jones GC. Angew. Chem. Int. Ed. 2012; 51: 9385
  • 47 Kang S.-K, Lee H.-W, Jang S.-B, Ho P.-S. J. Org. Chem. 1996; 61: 4720
  • 48 Edwards HJ, Hargrave JD, Penrose SD, Frost CG. Chem. Soc. Rev. 2010; 39: 2093
  • 49 Quach TD, Batey RA. Org. Lett. 2003; 5: 4397
  • 50 Yoshida S, Shimomori K, Nonaka T, Hosoya T. Chem. Lett. 2015; 44: 1324
  • 51 Yoshida S, Sugimura Y, Hazama Y, Nishiyama Y, Yano T, Shimizu S, Hosoya T. Chem. Commun. 2015; 51: 16613
  • 52 Hosoya and co-workers also used the Suzuki reactivity of 5b to prepare a substrate for a new thioamination reaction involving arynes; see: Yoshida S, Yano T, Misawa Y, Sugimura Y, Igawa K, Shimizu S, Tomooka K, Hosoya T. J. Am. Chem. Soc. 2015; 14071