Hydroboration of Vinyl Arenes Using SiO₂-Supported Rhodium Catalysts

Abstract

The metal-catalyzed hydroboration of vinyl arenes using catecholborane (HBcat) and pinacolborane (HBpin) has been examined with SiO₂-supported rhodium catalysts. Reactions with simple vinyl arenes (ArCH=CH₂) and HBcat using Rh(acac)(coe)₂ (coe = cyclooctene) gave selective formation of the corresponding branched isomers [ArCH(Bcat)Me]. Catalyst systems could be reused with no appreciable loss in activity or selectivity.

catalysis - heterogeneous - hydroborations - rhodium - silica support

References and Notes

<A NAME="RS06708ST-1A">1a</A> Brown HC. Kramer GW. Levy AB. Midland MM. Organic Syntheses via Boranes   Wiley-Interscience; New York: 1975. 

<A NAME="RS06708ST-1B">1b</A> Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 

<A NAME="RS06708ST-2A">2a</A> Männig D. Nöth H. Angew. Chem., Int. Ed. Engl.  1985,  24:  878 

<A NAME="RS06708ST-2B">2b</A> Beletskaya I. Pelter A. Tetrahedron  1997,  53:  4957 

<A NAME="RS06708ST-2C">2c</A> Kadlecek DE. Carroll PJ. Sneddon LG. J. Am. Chem. Soc.  2000,  122:  10868 

<A NAME="RS06708ST-2D">2d</A> Widauer C. Grützmacher H. Ziegler T. Organometallics  2000,  19:  2097 

<A NAME="RS06708ST-2E">2e</A> Huang X. Lin Z. Computational Modeling of Homogeneous Catalysis   Maseras F. Lledos A. Kluwer Academic; Amsterdam: 2002.  p.189-212  

<A NAME="RS06708ST-2F">2f</A> Crudden CM. Edwards D. Eur. J. Org. Chem.  2003,  4695 

<A NAME="RS06708ST-2G">2g</A> Carroll A.-M. O’Sullivan TP. Guiry PJ. Adv. Synth. Catal.  2005,  347:  609 

<A NAME="RS06708ST-2H">2h</A> Vogels CM. Westcott SA. Curr. Org. Chem.  2005,  9:  687 

<A NAME="RS06708ST-3A">3a</A> Kono H. Ito K. Nagai Y. Chem. Lett.  1975,  1095 

<A NAME="RS06708ST-3B">3b</A> Westcott SA. Blom HP. Marder TB. Baker RT. Calabrese JC. Inorg. Chem.  1993,  32:  2175 

<A NAME="RS06708ST-4">4</A> Dorigo AE. von Ragué Schleyer P. Angew. Chem., Int. Ed. Engl.  1995,  34:  115 

<A NAME="RS06708ST-5A">5a</A> Westcott SA. Blom HP. Marder TB. Baker RT. J. Am. Chem. Soc.  1992,  114:  8863 

<A NAME="RS06708ST-5B">5b</A> Brown JM. Lloyd-Jones GC. J. Chem. Soc., Chem. Commun.  1992,  710 

<A NAME="RS06708ST-5C">5c</A> Musaev DG. Mebel AM. Morokuma K. J. Am. Chem. Soc.  1994,  116:  10693 

<A NAME="RS06708ST-5D">5d</A> Coapes RB. Souza FES. Thomas RL. Hall JJ. Marder TB. Chem. Commun.  2003,  614 

<A NAME="RS06708ST-6A">6a</A> Hayashi T. Matsumoto Y. Ito Y. Tetrahedron: Asymmetry  1991,  2:  601 

<A NAME="RS06708ST-6B">6b</A> Lam WH. Lam KC. Lin Z. Shimada S. Perutz RN. Marder TB. Dalton Trans.  2004,  1556 

<A NAME="RS06708ST-7A">7a</A> Guiry PJ. McCarthy M. Lacey PM. Saunders CP. Kelly S. Connolly DJ. Curr. Org. Chem.  2000,  4:  821 

<A NAME="RS06708ST-7B">7b</A> Demay S. Volant F. Knochel P. Angew. Chem. Int. Ed.  2001,  40:  1235 

<A NAME="RS06708ST-7C">7c</A> Betley TA. Peters JC. Angew. Chem. Int. Ed.  2003,  42:  2385 

<A NAME="RS06708ST-7D">7d</A> Segarra AM. Daura-Oller E. Claver C. Poblet JM. Bo C. Fernández E. Chem. Eur. J.  2004,  10:  6456 

<A NAME="RS06708ST-7E">7e</A> Connolly DJ. Lacey PM. McCarthy M. Saunders CP. Carroll A.-M. Goddard R. Guiry PJ. J. Org. Chem.  2004,  69:  6572 

<A NAME="RS06708ST-7F">7f</A> Daura-Oller E. Segarra AM. Poblet JM. Claver C. Fernández E. Bo C. J. Org. Chem.  2004,  69:  2669 

<A NAME="RS06708ST-8A">8a</A> Juliette JJJ. Horváth IT. Gladysz JA. Angew. Chem., Int. Ed. Engl.  1997,  36:  1610 

<A NAME="RS06708ST-8B">8b</A> Juliette JJJ. Rutherford D. Horváth IT. Gladysz JA. J. Am. Chem. Soc.  1999,  121:  2696 

<A NAME="RS06708ST-8C">8c</A> Taylor RA. Santora BP. Gagné MR. Org. Lett.  2000,  2:  1781 

<A NAME="RS06708ST-8D">8d</A> Carter CAG. Baker RT. Nolan SP. Tumas W. Chem. Commun.  2000,  347 

<A NAME="RS06708ST-8E">8e</A> Köllner C. Togni A. Can. J. Chem.  2001,  79:  1762 

<A NAME="RS06708ST-8F">8f</A> Segarra AM. Guerrero C. Claver C. Fernández E. Chem. Commun.  2001,  1808 

<A NAME="RS06708ST-8G">8g</A> Segarra AM. Guerrero R. Claver C. Fernández E. Chem. Eur. J.  2003,  9:  191 

<A NAME="RS06708ST-8H">8h</A> Segarra AM. Guirado F. Claver C. Fernández E. Tetrahedron: Asymmetry  2003,  14:  1611 

<A NAME="RS06708ST-9A">9a</A> Chen R. Bronger RPJ. Kamer PCJ. van Leeuwen PWNM. Reek JNH. J. Am. Chem. Soc.  2004,  126:  14557 

<A NAME="RS06708ST-9B">9b</A> Huang L. Kawi S. J. Mol. Catal. A: Chem.  2004,  211:  23 

<A NAME="RS06708ST-9C">9c</A> Standfest-Hauser CM. Lummerstorfer T. Schmid R. Hoffmann H. Kirchner K. Puchberger M. Trzeciak AM. Mieczyńska E. Tylus W. Ziókowski JJ. J. Mol. Catal. A: Chem.  2004,  210:  179 

<A NAME="RS06708ST-9D">9d</A> Marchetti M. Paganelli S. Viel E. J. Mol. Catal. A: Chem.  2004,  222:  143 

<A NAME="RS06708ST-9E">9e</A> Bektesevic S. Tack T. Mason MR. Abraham MA. Ind. Eng. Chem. Res.  2005,  44:  4973 

<A NAME="RS06708ST-9F">9f</A> Wilkinson MJ. van Leeuwen PWNM. Reek JNH. Org. Biomol. Chem.  2005,  3:  2371 

<A NAME="RS06708ST-9G">9g</A> Debono N. Djakovitch L. Pinel C. J. Organomet. Chem.  2006,  691:  741 

<A NAME="RS06708ST-10A">10a</A> Cipot J. Vogels CM. McDonald R. Westcott SA. Stradiotto M. Organometallics  2006,  25:  5965 

<A NAME="RS06708ST-10B">10b</A> Geier SJ. Chapman EE. McIsaac DI. Vogels CM. Decken A. Westcott SA. Inorg. Chem. Commun.  2006,  9:  788 

<A NAME="RS06708ST-10C">10c</A> McIsaac DI. Geier SJ. Vogels CM. Decken A. Westcott SA. Inorg. Chim. Acta  2006,  359:  2771 

<A NAME="RS06708ST-10D">10d</A> Vogels CM. Decken A. Westcott SA. Can. J. Chem.  2006,  84:  146 

<A NAME="RS06708ST-11">11</A>

Si-DPP (R39030B) is available at SiliCycle (www.silicycle.com).

<A NAME="RS06708ST-12">12</A>

Experimental Procedure
In a typical experiment, a THF (0.5 mL) solution of Rh(acac)(coe)₂ (8 mg, 0.019 mmol) was added to a THF (2 mL) slurry of Si-DPP (60 mg, 0.056 mmol), and the mixture was stirred for 5 h. To this mixture was added a THF (0.5 mL) solution of 2-vinylnaphthalene (135 mg, 0.87 mmol) followed by a THF (0.5 mL) solution of HBcat (126 mg, 1.05 mmol). The reaction was allowed to proceed for 18 h at which point the mixture was filtered through a small plug of Celite before solvent was removed under vacuum. The residual oil was dissolved in C₆D₆ (1 mL) and analyzed by multinuclear NMR spectroscopy.^5a,¹0 Confirmation of product formation was carried out using GC-MS on products derived from a basic, oxidative workup.
Selected NMR Spectroscopic Data 4-MeOC₆H₄CH(Bcat)Me (i; R = OMe; Bcat): ^¹H NMR (270 MHz, C₆D₆): δ = 2.74 [q, J = 7.7 Hz, CH(Bcat)CH₃], 1.48 [d, J = 7.7 Hz, CH(Bcat)CH ₃].
4-MeOC₆H₄CH₂CH₂ (Bcat) (ii; R = OMe; Bcat): ^¹H NMR (270 MHz, C₆D₆): δ = 2.79 [t, J = 7.9 Hz, CH ₂CH₂ (Bcat)], 1.42 [t, J = 7.9 Hz, CH₂CH ₂ (Bcat)].
4-MeOC₆H₄CH=CH(Bcat) (iii; R = OMe; Bcat): ^¹H NMR (270 MHz, C₆D₆): δ = 7.82 [d, J = 18.3 Hz, CH=CH(Bcat)], 6.34 [d, J = 18.3 Hz, CH=CH(Bcat)].
4-MeOC₆H₄CH₂CH(Bcat)₂ (iv; R = OMe; Bcat): ^¹H NMR (270 MHz, C₆D₆): δ = 3.36 [d, J = 8.2 Hz, CH ₂CH(Bcat)₂], 2.11 [t, J = 8.2 Hz, CH₂CH(Bcat)₂].
4-FC₆H₄CH(Bcat)Me (i; R = F; Bcat): ^¹H NMR (270 MHz, C₆D₆): δ = 2.60 [q, J = 7.7 Hz, CH(Bcat)CH₃), 1.36 [d, J = 7.7 Hz, CH(Bcat)CH ₃].
4-FC₆H₄CH=CH(Bcat) (iii; R = F; Bcat): ^¹H NMR (270 MHz, C₆D₆): δ = 7.62 [d, J = 18.3 Hz, CH=CH(Bcat)], 6.23 [d, J = 18.3 Hz, CH=CH(Bcat)].
4-FC₆H₄CH₂CH(Bcat)₂ (iv; R = F; Bcat): ^¹H NMR (270 MHz, C₆D₆): δ = 3.22 [d, J = 8.2 Hz, CH ₂CH(Bcat)₂], 1.99 [t, J = 8.2 Hz, CH₂CH(Bcat)₂].

<A NAME="RS06708ST-13A">13a</A> Brown JM. Lloyd-Jones GC. J. Chem. Soc., Chem. Commun.  1992,  710 

<A NAME="RS06708ST-13B">13b</A> Westcott SA. Marder TB. Baker RT. Organometallics  1993,  12:  975 

<A NAME="RS06708ST-13C">13c</A> Baker RT. Calabrese JC. Westcott SA. Nguyen P. Marder TB. J. Am. Chem. Soc.  1993,  115:  4367 

<A NAME="RS06708ST-13D">13d</A> Brown JM. Lloyd-Jones GC. J. Am. Chem. Soc.  1994,  116:  866 

<A NAME="RS06708ST-13E">13e</A> Motry DH. Smith MR. J. Am. Chem. Soc.  1995,  117:  6615 

<A NAME="RS06708ST-13F">13f</A> Motry DH. Brazil AG. Smith MR. J. Am. Chem. Soc.  1997,  119:  2743 

<A NAME="RS06708ST-13G">13g</A> Murata M. Watanabe S. Masuda Y. Tetrahedron Lett.  1999,  40:  2585 

<A NAME="RS06708ST-13H">13h</A> Waltz KM. Muhoro CN. Hartwig JF. Organometallics  1999,  18:  3383 

<A NAME="RS06708ST-13I">13i</A> Vogels CM. Hayes PG. Shaver MP. Westcott SA. Chem. Commun.  2000,  51 

<A NAME="RS06708ST-13J">13j</A> Kadlecek DE. Carroll PJ. Sneddon LG. J. Am. Chem. Soc.  2000,  122:  10868 

<A NAME="RS06708ST-13K">13k</A> Murata M. Kawakita K. Asana T. Watanabe S. Masuda Y. Bull. Chem. Soc. Jpn.  2002,  75:  825 

<A NAME="RS06708ST-13L">13l</A> Caballero A. Sabo-Etienne S. Organometallics  2007,  26:  1191 

<A NAME="RS06708ST-13M">13m</A> Molinos E. Brayshaw SK. Kociok-Köhn G. Weller AS. Organometallics  2007,  26:  2370 

<A NAME="RS06708ST-13N">13n</A> Mkhalid IAI. Coapes RB. Edes SN. Coventry DN. Souza FES. Thomas RL. Hall JJ. Bi S.-W. Lin Z. Marder TB. Dalton Trans.  2008,  1055 

<A NAME="RS06708ST-14">14</A> Burke JM. Coates RB. Goeta AE. Howard JAK. Marder TB. Robins EG. Westcott SA. J. Organomet. Chem.  2002,  649:  199 

<A NAME="RS06708ST-15">15</A> Burgess K. van der Donk WA. Westcott SA. Marder TB. Baker RT. Calabrese JC. J. Am. Chem. Soc.  1992,  114:  9350 

<A NAME="RS06708ST-16">16</A>

Selected NMR Spectroscopic Data
4-MeOC₆H₄CH(Bpin)Me (i; R = OMe; Bpin): ^¹H NMR (270 MHz, C₆D₆): δ = 2.56 [q, J = 7.7 Hz, CH(Bpin)CH₃], 1.50 [d, J = 7.7 Hz, CH(Bpin)CH ₃].
4-MeOC₆H₄CH₂CH₂(Bpin) (ii; R = OMe; Bpin): ^¹H NMR (270 MHz, C₆D₆): δ = 2.87 [t, J = 7.9 Hz, CH ₂CH₂ (Bpin)], 1.12 [t, J = 7.9 Hz, CH₂CH ₂(Bpin)].
4-MeOC₆H₄CH=CH(Bpin) (iii; R = OMe; Bpin): ^¹H NMR (270 MHz, C₆D₆): δ = 7.80 [d, J = 18.3 Hz, CH=CH(Bpin)], 6.40 [d, J = 18.3 Hz, CH=CH(Bpin)].
4-FC₆H₄CH(Bpin)Me (i; R = F; Bpin): ^¹H NMR (270 MHz, C₆D₆): δ = 2.45 [q, J = 7.7 Hz, CH(Bpin)CH₃], 1.38 [d, J = 7.7 Hz, CH(Bpin)CH ₃].
4-FC₆H₄CH₂CH₂(Bpin) (ii; R = F; Bpin): ^¹H NMR (270 MHz, C₆D₆): δ = 2.70 [t, J = 8.1 Hz, CH ₂CH₂ (Bpin)], 1.12 [t, J = 8.1 Hz, CH₂CH ₂(Bpin)].
4-FC₆H₄CH=CH(Bpin) (iii; R = F; Bpin): ^¹H NMR (270 MHz, C₆D₆): δ = 7.60 [d, J = 18.5 Hz, CH=CH(Bpin)], 6.27 [d, J = 18.5 Hz, CH=CH(Bpin)].
4-FC₆H₄CH₂CH(Bpin)₂ (iv; R = F; Bpin): ^¹H NMR (270 MHz, C₆D₆): δ = 3.11 [d, J = 8.2 Hz, CH ₂CH(Bpin)₂], 1.50 [t, J = 8.2 Hz, CH₂CH(Bpin)₂].
PhCH(Bpin)Me (i; R = H; Bpin): ^¹H NMR (270 MHz, C₆D₆): δ = 2.51 [q, J = 7.4 Hz, CH(Bpin)CH₃], 1.42 [d, J = 7.4 Hz, CH(Bpin)CH ₃].
PhCH₂CH₂(Bpin) (ii; R = H; Bpin): ^¹H NMR (270 MHz, C₆D₆): δ = 2.80 [t, J = 8.0 Hz, CH ₂CH₂ (Bpin)], 1.03 [t, J = 8.0 Hz, CH₂CH ₂ (Bpin)].
PhCH=CH(Bpin) (iii; R = H; Bpin): ^¹H NMR (270 MHz, C₆D₆): δ =7.70 [d, J = 18.5 Hz, CH=CH(Bpin)], 6.40 [d, J = 18.5 Hz, CH=CH(Bpin)].
PhCH₂CH(Bpin)₂ (iv; R = H; Bpin): ^¹H NMR (270 MHz, C₆D₆): δ = 3.20 [d, J = 8.0 Hz, CH ₂CH(Bpin)₂], 1.30 [t, J = 8.0 Hz, CH₂CH(Bpin)₂].

<A NAME="RS06708ST-17A">17a</A> Pereira S. Srebnik M. Organometallics  1995,  14:  3127 

<A NAME="RS06708ST-17B">17b</A> Zheng B. Srebnik M. J. Org. Chem.  1995,  60:  486 

<A NAME="RS06708ST-17C">17c</A> Pereira S. Srebnik M. Tetrahedron Lett.  1996,  37:  3283 

<A NAME="RS06708ST-17D">17d</A> Ramachandran PV. Jennings MP. Brown HC. Org. Lett.  1999,  1:  1399 

<A NAME="RS06708ST-17E">17e</A> Ohmura T. Yamamoto Y. Miyaura N. J. Am. Chem. Soc.  2000,  122:  4990 

<A NAME="RS06708ST-17F">17f</A> Segarra AM. Claver C. Fernández E. Chem. Commun.  2001,  464 

<A NAME="RS06708ST-17G">17g</A> Hoffman RW. Krüger J. Brückner D. New J. Chem.  2001,  25:  102 

<A NAME="RS06708ST-17H">17h</A> Rubina M. Rubin M. Gevorgyan V. J. Am. Chem. Soc.  2003,  125:  7198 

<A NAME="RS06708ST-17I">17i</A> Yamamoto Y. Fujikawa R. Umemoto T. Miyaura N. Tetrahedron  2004,  60:  10695 

<A NAME="RS06708ST-17J">17j</A> Rubin M. Gevorgyan V. Synthesis  2004,  796 

<A NAME="RS06708ST-17K">17k</A> Lee T. Baik C. Jung I. Song KH. Kim S. Kim D. Kang SO. Ko J. Organometallics  2004,  23:  4569 

<A NAME="RS06708ST-17L">17l</A> Crudden CM. Hleba YB. Chen AC. J. Am. Chem. Soc.  2004,  126:  9200 

<A NAME="RS06708ST-17M">17m</A> Horino Y. Livinghouse T. Stan M. Synlett  2004,  2639 

<A NAME="RS06708ST-17N">17n</A> Wang YD. Kimball G. Prashad AS. Wang Y. Tetrahedron Lett.  2005,  46:  8777 

<A NAME="RS06708ST-17O">17o</A> Edwards DE. Crudden CM. Adv. Synth. Catal.  2005,  347:  50 

<A NAME="RS06708ST-17P">17p</A> Moteki SA. Wu D. Chandra KL. Reddy DS. Takacs JM. Org. Lett.  2006,  8:  3097 

<A NAME="RS06708ST-17Q">17q</A> Hadebe SW. Robinson RS. Tetrahedron Lett.  2006,  47:  1299 

<A NAME="RS06708ST-17R">17r</A> Hadebe SW. Robinson RS. Eur. J. Org. Chem.  2006,  4898 

<A NAME="RS06708ST-17S">17s</A> Kinder RE. Widenhoefer RA. Org. Lett.  2006,  8:  1967 

<A NAME="RS06708ST-17T">17t</A> Ghebreyessus KY. Angelici RJ. Organometallics  2006,  25:  3040 

<A NAME="RS06708ST-17U">17u</A> Scurto AM. Leitner W. Chem. Commun.  2006,  3681 

<A NAME="RS06708ST-17V">17v</A> Onodera G. Nishibayashi Y. Uemura S. Organometallics  2006,  25:  35 

<A NAME="RS06708ST-17W">17w</A> Wechsler D. Rankin MA. McDonald R. Ferguson MJ. Schatte G. Stradiotto M. Organometallics  2007,  26:  6418 

<A NAME="RS06708ST-17X">17x</A> Moteki SA. Takacs JM. Angew. Chem. Int. Ed.  2008,  47:  894 

<A NAME="RS06708ST-18">18</A>

Selected NMR Spectroscopic Data
2,4,6-Me₃C₆H₂CH(Bcat)Me (v): ^¹H NMR (270 MHz, C₆D₆): δ = 2.90 [q, J = 7.7 Hz, CH(Bcat)CH₃], 1.42 [d, J = 7.7 Hz, CH(Bcat)CH ₃].
2,4,6-Me₃C₆H₂CH₂CH₂(Bcat) (vi): ^¹H NMR (270 MHz, C₆D₆): δ = 2.81 [t, J = 7.9 Hz, CH ₂CH₂ (Bcat)], 1.31 [t, J = 7.9 Hz, CH₂CH ₂ (Bcat)].
2,4,6-Me₃C₆H₂CH=CH(Bcat) (vii): ^¹H NMR (270 MHz, C₆D₆): δ = 7.90 [d, J = 18.3 Hz, CH=CH(Bcat)], 6.10 [d, J = 18.3 Hz, CH=CH(Bcat)].
2,4,6-Me₃C₆H₂CH₂CH(Bcat)₂ (viii): ^¹H NMR (270 MHz, C₆D₆): δ = 3.41 [d, J = 8.2 Hz, CH ₂CH(Bcat)₂], 2.11 [t, J = 8.2 Hz, CH₂CH(Bcat)₂].