Gold-Catalyzed Direct Amination of Allylic Alcohols

Abstract

An efficient and direct synthesis of allylic amines from allylic alcohols was developed by utilization of gold complexes as catalysts under mild reaction conditions. AuCl₃ proved to be a better catalyst than a cationic gold(I) complex of AuCl(PPh₃)/AgOTf.

gold catalysis - allylic alcohols - amination - nucleophilic substitution - synthetic methods

References and Notes

For reviews, see:

<A NAME="RW25406ST-1A">1a</A> Tsuji J. Palladium Reagents and Catalysis   John Wiley and Sons; Chichester: 2004. 

<A NAME="RW25406ST-1B">1b</A> Nakamura I. Yamamoto Y. Chem. Rev.  2004,  104:  2127 

<A NAME="RW25406ST-1C">1c</A> Tsuji J. Transition Metal Reagents and Catalysts   John Wiley and Sons; New York: 2000. 

<A NAME="RW25406ST-1D">1d</A> Transition Metals for Organic Synthesis   Beller M. Bolm C. Wiley-VCH; Weinheim: 1998. 

<A NAME="RW25406ST-1E">1e</A> Trost BM. Crawley ML. Chem. Rev.  2003,  103:  2921 

For reviews, see:

<A NAME="RW25406ST-2A">2a</A> Godleski SA. In Comprehensive Organic Synthesis   Vol. 4:  Trost BM. Fleming I. Pergamon Press; New York: 1991.  p.585 

<A NAME="RW25406ST-2B">2b</A> Davis JA. In Comprehensive Organometallic Chemistry II   Vol. 9:  Abel EW. Stone FGA. Wilkinson G. Pergamon; Oxford: 1995.  p.291 

<A NAME="RW25406ST-2C">2c</A> Johannsen M. Jørgensen KA. Chem. Rev.  1998,  98:  1689 

<A NAME="RW25406ST-2D">2d</A> Trost BM. VanVranken DL. Chem. Rev.  1996,  96:  395 

Selected papers:

<A NAME="RW25406ST-3A">3a</A> Tsuji M. Minami I. Acc. Chem. Res.  1987,  20:  140 

<A NAME="RW25406ST-3B">3b</A> Trost BM. Angew. Chem., Int. Ed. Engl.  1989,  28:  1173 

<A NAME="RW25406ST-3C">3c</A> Tsuji J. Synthesis  1990,  739 

<A NAME="RW25406ST-3D">3d</A> Uozumi Y. Danjo H. Hayashi T. J. Org. Chem.  1999,  64:  3384 

Selected papers:

<A NAME="RW25406ST-4A">4a</A> Goux C. Massacret M. Lhoste P. Sinou D. Organometallics  1995,  14:  4585 

<A NAME="RW25406ST-4B">4b</A> Deardorff DR. Savin KA. Justman CJ. Karanjawala ZE. Sheppeck JE. Hager DC. Aydin N. J. Org. Chem.  1996,  61:  3616 

<A NAME="RW25406ST-4C">4c</A> Moreno-Mañas M. Morral L. Pleixats R. J. Org. Chem.  1998,  63:  6160 

<A NAME="RW25406ST-5A">5a</A> Ziegler FE. Kneisley A. Wester RT. Tetrahedron Lett.  1986,  27:  1221 

<A NAME="RW25406ST-5B">5b</A> Ziegler FE. Cain WT. Kneisley A. Stirchak EP. Wester RT. J. Am. Chem. Soc.  1988,  110:  5442 

<A NAME="RW25406ST-6A">6a</A> Connell RD. Rein T. Åkermark B. Helquist P. J. Org. Chem.  1988,  53:  3845 

<A NAME="RW25406ST-6B">6b</A> Sakamoto M. Shimizu I. Yamamoto A. Bull. Chem. Soc. Jpn.  1996,  69:  1065 

Selected papers:

<A NAME="RW25406ST-7A">7a</A> Tamura R. Kai Y. Kakihama M. Hayashi K. Tsuji M. Nakamura T. Oda D. J. Org. Chem.  1986,  51:  4375 

<A NAME="RW25406ST-7B">7b</A> Tamura R. Kato M. Saegusa K. Kakihama M. Oda D. J. Org. Chem.  1987,  52:  4121 

<A NAME="RW25406ST-7C">7c</A> Tamura R. Kamimura A. Ono N. Synthesis  1991,  423 

For review, see:

<A NAME="RW25406ST-8A">8a</A> Muzart J. Tetrahedron  2005,  61:  4179 

See also:

<A NAME="RW25406ST-8B">8b</A> Lumin S. Falck JR. Capdevila J. Karara A. Tetrahedron Lett.  1992,  33:  2091 

<A NAME="RW25406ST-8C">8c</A> Tsay S. Lin LC. Furth PA. Shum CC. King DB. Yu SF. Chen B. Hwu JR. Synthesis  1993,  329 

<A NAME="RW25406ST-8D">8d</A> Masuyama Y. Kagawa M. Kurusu Y. Chem. Lett.  1995,  1121 

<A NAME="RW25406ST-8E">8e</A> Hirai Y. Shibuya K. Fukuda Y. Yokoyama H. Yamaguchi S. Chem. Lett.  1997,  221 

<A NAME="RW25406ST-9A">9a</A> Itoh K. Hamaguchi N. Miura M. Nomura M. J. Chem. Soc., Perkin Trans. 1  1992,  2833 

<A NAME="RW25406ST-9B">9b</A> Satoh T. Ikeda M. Miura M. Nomura M. J. Org. Chem.  1997,  62:  4877 

<A NAME="RW25406ST-9C">9c</A> Yang S.-C. Hung C.-W. J. Org. Chem.  1999,  64:  5000 

<A NAME="RW25406ST-9D">9d</A> Shue Y.-J. Yang S.-C. Lai H.-C. Tetrahedron Lett.  2003,  44:  1481 

<A NAME="RW25406ST-10A">10a</A> Kimura M. Horino Y. Mukai R. Tanaka S. Tamaru Y. J. Am. Chem. Soc.  2001,  123:  10401 

<A NAME="RW25406ST-10B">10b</A> Kimura M. Futamata M. Shibata K. Tamaru Y. Chem. Commun.  2003,  234 

<A NAME="RW25406ST-10C">10c</A> Kimura M. Tomizawa T. Horino Y. Tanaka S. Tamaru Y. Tetrahedron Lett.  2000,  41:  3627 

<A NAME="RW25406ST-11">11</A> Stary I. Stará IG. Kocovsky P. Tetrahedron Lett.  1993,  34:  179 

<A NAME="RW25406ST-12A">12a</A> Masuyama Y. Takahara JP. Kurusu Y. J. Am. Chem. Soc.  1988,  110:  4473 

<A NAME="RW25406ST-12B">12b</A>

See also reference 8d.

<A NAME="RW25406ST-13">13</A> Lu X. Lu L. Sun J. J. Mol. Catal.  1987,  41:  245 

<A NAME="RW25406ST-14">14</A> Sakamoto M. Shimizu I. Yamamoto A. Bull. Chem. Soc. Jpn.  1996,  69:  1065 

<A NAME="RW25406ST-15A">15a</A> Ozawa F. Okamoto H. Kawagishi S. Yamamoto S. Minami T. Yoshifuji M. J. Am. Chem. Soc.  2002,  124:  10968 

<A NAME="RW25406ST-15B">15b</A> Ozawa F. Yoshifuji M. Dalton Trans.  2006,  4987 

<A NAME="RW25406ST-16">16</A> Yasuda M. Somyo T. Baba A. Angew. Chem. Int. Ed.  2006,  45:  793 

<A NAME="RW25406ST-17">17</A> Sanz R. Martínez A. Miguel D. Álvarez-Gutiérrez JM. Rodríguez F. Adv. Synth. Catal.  2006,  348:  1841 

<A NAME="RW25406ST-18">18</A> During this manuscript preparation, a bismuth-catalyzed allylic substitution was reported. In this reaction, the additives such as KPF₆ were usually required: Qin H. Yamagiwa N. Matsunaga S. Shibasaki M. Angew. Chem. Int. Ed.  2006,  46:  409 

For reviews on gold-catalyzed reactions, see:

<A NAME="RW25406ST-19A">19a</A> Dyker G. Angew. Chem. Int. Ed.  2000,  39:  4237 

<A NAME="RW25406ST-19B">19b</A> Hashmi ASK. Gold Bull.  2003,  36:  3 

<A NAME="RW25406ST-19C">19c</A> Hashmi ASK. Gold Bull.  2004,  37:  51 

<A NAME="RW25406ST-19D">19d</A> Hoffmann-Röder A. Krause N. Org. Biomol. Chem.  2005,  3:  387 

<A NAME="RW25406ST-19E">19e</A> Hashmi ASK. Angew. Chem. Int. Ed.  2005,  44:  6990 

<A NAME="RW25406ST-19F">19f</A> Ma S. Yu S. Gu Z. Angew. Chem. Int. Ed.  2006,  45:  200 

<A NAME="RW25406ST-20A">20a</A> Liu Y. Song F. Guo S. J. Am. Chem. Soc.  2006,  128:  11332 

<A NAME="RW25406ST-20B">20b</A> Liu Y. Liu M. Guo S. Tu H. Zhou Y. Gao H. Org. Lett.  2006,  8:  3445 

<A NAME="RW25406ST-20C">20c</A> Liu Y. Song F. Song Z. Liu M. Yan B. Org. Lett.  2005,  7:  5409 

<A NAME="RW25406ST-21">21</A> Liu Y. Song F. Cong L. J. Org. Chem.  2005,  70:  6999 

<A NAME="RW25406ST-22">22</A> Guo S. Zhang H. Song F. Liu Y. Tetrahedron  2007,  63:  2009 

For gold-catalyzed substitution of propargylic, and/or benzylic alcohols, see:

<A NAME="RW25406ST-23A">23a</A> Georgy M. Boucard V. Campagne J.-M. J. Am. Chem. Soc.  2005,  127:  14180 

<A NAME="RW25406ST-23B">23b</A> Terrasson V. Marque S. Georgy M. Campagne J.-M. Adv. Synth. Catal.  2006,  348:  2063 

For gold-catalyzed addition of amines to olefins, allenes or alkynes, see:

<A NAME="RW25406ST-24A">24a</A> Zhang J. Yang C. He C. J. Am. Chem. Soc.  2006,  128:  1798 

<A NAME="RW25406ST-24B">24b</A> Brouwer C. He C. Angew. Chem. Int. Ed.  2006,  45:  1744 

<A NAME="RW25406ST-24C">24c</A> Han X. Widenhoefer RA. Angew. Chem. Int. Ed.  2006,  45:  1747 

<A NAME="RW25406ST-24D">24d</A> Nishina N. Yamamoto Y. Angew. Chem. Int. Ed.  2006,  45:  3314 

<A NAME="RW25406ST-24E">24e</A> Patil NT. Lutete LM. Nishina N. Yamamoto Y. Tetrahedron Lett.  2006,  47:  4749 

<A NAME="RW25406ST-24F">24f</A> Zhang Z. Liu C. Kinder R. Han X. Qian H. Widenhoefer RA. J. Am. Chem. Soc.  2006,  128:  9066 

<A NAME="RW25406ST-24G">24g</A> Morita N. Krause N. Org. Lett.  2004,  6:  4121 

<A NAME="RW25406ST-24H">24h</A> Alfonsi M. Arcadi A. Aschi M. Bianchi G. Marinelli F. J. Org. Chem.  2005,  70:  2265 

<A NAME="RW25406ST-24I">24i</A> Arcadi A. Bianchi G. Marinelli F. Synthesis  2004,  610 

<A NAME="RW25406ST-24J">24j</A> Mizushima E. Hayashi T. Tanaka M. Org. Lett.  2003,  5:  3349 

<A NAME="RW25406ST-25A">25a</A> Terrasson V. Marque S. Georgy M. Campagne J. Prima D. Adv. Synth. Catal.  2006,  348:  2063 

<A NAME="RW25406ST-25B">25b</A> Liu J. Muth E. Flörke U. Henkel G. Merz K. Sauvageau J. Schwake E. Dyker G. Adv. Synth. Catal.  2006,  348:  456 

<A NAME="RW25406ST-26">26</A>

Typical Procedure for AuCl ₃ -Catalyzed Direct Amination of Allylic Alcohols
A solution of AuCl₃ in MeCN (0.05 M) was prepared. Under N₂ atmosphere, 1,3-diphenylprop-2-en-1-ol (1a, 0.11 g, 0.5 mmol) and p-ClC₆H₄NH₂ (0.13 g, 1 mmol) were added to a 25 mL round-bottomed flask containing a stirring bar, and then 5 mL MeCN was added. To the mixture, 0.2 mL AuCl₃ (0.01 mmol) was added. The resulting solution was stirred at 50 °C until the reaction was completed as monitored by thin-layer chromatography (3 h). The solvent was removed in vacuo and the residue was purified by flash chromatography on silica gel (PE-EtOAc = 30:1) afforded product 2c in 92% isolated yield.
N-(E)-(4-Chlorophenyl)-(1,3-diphenylallyl)amine (2c): ¹H NMR (CDCl₃, TMS): δ = 4.12 (br s, 1 H), 5.02 (d, J = 5.7 Hz, 1 H), 6.35 (dd, J = 6.0, 15.9 Hz, 1 H), 6.50-6.61 (m, 3 H), 7.04-7.09 (m, 2 H), 7.19-7.41 (m, 10 H). ¹³C NMR (CDCl₃, TMS): δ = 60.65, 114.64, 122.23, 126.48, 127.13, 127.67, 127.77, 128.56, 128.87, 128.93, 130.12, 131.25, 136.40, 141.53, 145.66. HRMS (EI): m/z calcd for C₂₁H₁₈ClN: 319.1128; found: 319.1121.