Unusual Regio- and Enantioselective [1,2]-Stevens Rearrangement of a Spirobi[dibenzazepinium] Cation

Abstract

Highly symmetric spirobi[dibenzazepinium] cation 3 reacts with P₄-t-Bu to form exclusively a ring-expanded tertiary amine; this unusual reactivity can be traced back to the geometry of the ylide.

ammonium - rearrangements - regioselectivity - stereoselectivity - ylides

References

<A NAME="RD10704TST-1A">1a</A> Dolling UH. Davis P. Grabowski EJJ. J. Am. Chem. Soc.  1984,  106:  446 

<A NAME="RD10704TST-1B">1b</A> Maruoka K. Ooi T. Chem. Rev.  2003,  103:  3013 

<A NAME="RD10704TST-1C">1c</A> Lygo B. Andrews BI. Acc. Chem. Res.  2004,  37:  in press

<A NAME="RD10704TST-2A">2a</A> Keller EK. Phase-Transfer Reactions   George Thieme Verlag; Stuttgart: 1987. 

<A NAME="RD10704TST-2B">2b</A> Makosza M. Fedorynski M. Adv. Catal.  1987,  35:  375 

<A NAME="RD10704TST-2C">2c</A> Goldberg Y. Phase Transfer Catalysis. Selected Problems and Applications   Gordon and Breach; Philadelphia PA: 1992. 

<A NAME="RD10704TST-2D">2d</A> Dehmlow EV. Dehmlow SS. Phase Transfer Catalysis   3rd ed.:  VCH; New York: 1993. 

<A NAME="RD10704TST-2E">2e</A> Starks CM. Liotta CL. Halpern M. Phase-Transfer Catalysis. Fundamentals, Applications, and Industrial Perspectives   Chapman and Hall; New York: 1994. 

<A NAME="RD10704TST-2F">2f</A> Makosza M. Fedorynski M. Pol. J. Chem.  1996,  70:  1093 

<A NAME="RD10704TST-2G">2g</A> Handbook of Phase Transfer Catalysis   Sasson Y. Neumann R. Blackie; London: 1997. 

<A NAME="RD10704TST-3">3</A> O’Donnell MJ. In Catalytic Asymmetric Synthesis   Ojima I. VCH; New York: 1993.  p.389-411  

<A NAME="RD10704TST-4A">4a</A> Corey EJ. Xu F. Noe MC. J. Am. Chem. Soc.  1997,  119:  12414 

<A NAME="RD10704TST-4B">4b</A> Lygo B. Wainwright PG. Tetrahedron Lett.  1997,  38:  8595 

<A NAME="RD10704TST-4C">4c</A> Park H.-G. Jeong B.-S. Yoo M.-S. Lee J.-H. Park M.-K. Lee Y.-J. Kim M.-J. Jew S.-S. Angew. Chem. Int. Ed.  2002,  41:  3036 

<A NAME="RD10704TST-4D">4d</A> Bhunnoo RA. Hu Y. Laine DI. Brown RCD. Angew. Chem. Int. Ed.  2002,  41:  3479 

<A NAME="RD10704TST-4E">4e</A> Ohshima T. Gnanadesikan V. Shibuguchi T. Fukuta Y. Nemoto T. Shibasaki M. J. Am. Chem. Soc.  2003,  125:  11206 

<A NAME="RD10704TST-5A">5a</A> Ooi T. Kameda M. Maruoka K. J. Am. Chem. Soc.  1999,  121:  6519 

<A NAME="RD10704TST-5B">5b</A> Ooi T. Kameda M. Maruoka K. J. Am. Chem. Soc.  1999,  121:  6519 

<A NAME="RD10704TST-5C">5c</A> Ooi T. Sakai D. Takeuchi M. Tayama E. Maruoka K. Angew. Chem. Int. Ed.  2003,  42:  5868 

<A NAME="RD10704TST-5D">5d</A> Lygo B. Allbutt B. James SR. Tetrahedron Lett.  2003,  44:  5629 

<A NAME="RD10704TST-5E">5e</A> Lygo B. Allbutt B. Synlett  2004,  326 

<A NAME="RD10704TST-6A">6a</A> Stevens TS. Creighton EM. Gordon AB. MacNicol M. J. Chem. Soc.  1928,  3193 

<A NAME="RD10704TST-6B">6b</A> Zaragoza F. Tetrahedron  1997,  53:  3425 

<A NAME="RD10704TST-6C">6c</A> Marko IE. In Comprehensive Organic Synthesis   Vol. 3:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991.  p.913-974  

<A NAME="RD10704TST-6D">6d</A> Harwood LM. Polar Rearrangements   Oxford University Press; New York: 1992. 

<A NAME="RD10704TST-7A">7a</A> Ollis WD. Rey M. Sutherland IO. Closs GL. J. Chem. Soc., Chem. Commun.  1975,  543 

<A NAME="RD10704TST-7B">7b</A> Ollis WD. Rey M. Sutherland IO. J. Chem. Soc., Perkin Trans. 1  1983,  1009 

<A NAME="RD10704TST-7C">7c</A> Chantrapromma K. Ollis WD. Sutherland IO. J. Chem. Soc., Perkin Trans. 1  1983,  1049 

<A NAME="RD10704TST-7D">7d</A> Maeda Y. Sato Y. J. Chem. Soc., Perkin Trans. 1  1997,  1491 

For recent examples of [1,2]-Stevens rearrangement, see:

<A NAME="RD10704TST-8A">8a</A> Pedrosa R. Andres C. Delgado M. Synlett  2000,  893 

<A NAME="RD10704TST-8B">8b</A> Chelucci G. Saba A. Valenti R. Bacchi A. Tetrahedron: Asymmetry  2000,  11:  3449 

<A NAME="RD10704TST-8C">8c</A> Liou JP. Cheng CY. Tetrahedron Lett.  2000,  41:  915 

<A NAME="RD10704TST-8D">8d</A> Padwa A. Beall LS. Eidell CK. Worsencroft KJ. J. Org. Chem.  2001,  66:  2414 

<A NAME="RD10704TST-8E">8e</A> Hanessian S. Mauduit M. Angew. Chem. Int. Ed.  2001,  40:  3810 

<A NAME="RD10704TST-8F">8f</A> Clark JS. Middleton MD. Org. Lett.  2002,  4:  765 

<A NAME="RD10704TST-8G">8g</A> Glaeske KW. Naidu BN. West FG. Tetrahedron: Asymmetry  2003,  14:  917 

<A NAME="RD10704TST-8H">8h</A> Harada M. Nakai T. Tomooka K. Synlett  2004,  365 

<A NAME="RD10704TST-9A">9a</A> Joshua H. Gans R. Mislow K. J. Am. Chem. Soc.  1968,  90:  4884 

<A NAME="RD10704TST-9B">9b</A> Stara IG. Stary I. Tichy M. Zavada J. Hanus V. J. Am. Chem. Soc.  1994,  116:  5084 

<A NAME="RD10704TST-10">10</A>

Bis(tetrachlorobenzenediolato) mono([1,1′]binaphthalenyl-2,2′-diolato)phosphate(V) anion: Lacour J., Londez A., Goujon-Ginglinger C., Buß V., Bernardinelli G.; Org. Lett.; 2000, 2: 4185

<A NAME="RD10704TST-11">11</A> Mikami K. Yamanaka M. Chem. Rev.  2003,  103:  3369 

<A NAME="RD10704TST-12">12</A> Vial L. Lacour J. Org. Lett.  2002,  4:  3939 

<A NAME="RD10704TST-13">13</A> Ooi T. Kubota Y. Maruoka K. Synlett  2003,  1931 

<A NAME="RD10704TST-14">14</A> Schwesinger R. Schlemper H. Angew. Chem., Int. Ed. Engl.  1987,  26:  1167 

<A NAME="RD10704TST-15">15</A>

Physical data for 4. R_f = 0.94 (basic Al₂O₃, Et₂O). ¹H NMR (500 MHz, CDCl₃, 233K): δ = 2.98 (dd, J = 13.56 Hz, J = 8.98 Hz,1 H), 3.24 (d, J = 8.98 Hz, 1 H), 3.34 (d, J = 13.56 Hz, 1 H), 3.49 (d, J = 13.71 Hz, 1 H), 3.91 (q _AB , Δν_AB = 41.45 Hz, J _AB = 14.19 Hz, 2 H), 4.07 (d, J = 13.71 Hz, 1 H), 7.09 (d, J = 7.41 Hz, 1 H), 7.27-7.55 (m, 3 H), 7.65 (d, J = 7.56 Hz, 1 H), 7.67 (d, J = 7.72 Hz, 1 H). ¹³C NMR (126 MHz, CDCl₃, 233K): δ = 38.1, 59.6, 62.3, 62.8, 126.3, 126.4, 126.9, 127.3, 127.4, 127.6, 127.7, 128.0, 128.0, 128.1, 128.5, 128.9, 129.1, 130.1, 130.7, 133.5, 138.7, 139.1, 139.5, 139.9, 140.1, 140.8, 141.0. IR (neat): 3061 (w), 3018 (w), 2923 (m), 2853 (m), 1481 (w), 1441 (m), 1361 (w), 1260 (w), 1191 (w), 1008 (w), 1081 (m), 941 (w), 801 (m), 746 (s) cm^-1. HRMS (EI): m/e calcd for C₂₂H₁₉N: 297.15175; found: 297.15084. The ee was measured using CSP-HPLC (Chiracel AD-H, 95/5 i-PrOH-n-hexane, 0.5 mL/min, 23 °C).

<A NAME="RD10704TST-16">16</A> For a preliminary report indicating the preferred formation of 4, see: Wittig G. König G. Clauss K. Liebigs Ann. Chem.  1955,  593:  127 

<A NAME="RD10704TST-17">17</A>

Crystal data for (C₂₈H₂₄N)⁺Cl^-(CHCl₃)_0.7: M = 493.5, monoclinic, P2₁/c, a = 16.4658 (14), b = 14.7628 (9), c = 10.7661 (8), β = 101.132 (10)º Å, U = 2567.8 (3) ų, T = 200 K, Z = 4, µ(MoK_α) = 0.384 mm^-1. The final R(F) = 0.046, wR(F) = 0.043 and S = 1.00(1). The CHCl₃ molecules are disordered on two distinct sites refined for global population parameters of 0.7 and are located on channels parallel to the [001] direction. CCDC 234418.

<A NAME="RD10704TST-18">18</A> Tichy M. Budesinsky M. Gunterova J. Zavada J. Podiaha J. Cisarova I. Tetrahedron  1999,  55:  7893 

<A NAME="RD10704TST-19">19</A> TRISPHAT is the common name for tris(tetrachloro-benzenediolato)phosphate(V) anion: Lacour J. Ginglinger C. Grivet C. Bernardinelli G. Angew. Chem., Int. Ed. Engl.  1997,  36:  608 

<A NAME="RD10704TST-20">20</A>

The deuterium atom is distributed evenly between the axial and equatorial positions due to the rapid interconversion of the atropisomers of 3.

<A NAME="RD10704TST-21">21</A>

Gaussian 98 (Revision A.7): Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian, Inc., Pittsburgh PA, 1998.

For reports on enantioselective [1,2]-Stevens rearrangement using ylide generated by the Rh(II) decomposition of chiral diazo compounds:

<A NAME="RD10704TST-22A">22a</A> West FG. Naidu BN. J. Am. Chem. Soc.  1994,  116:  8420 

<A NAME="RD10704TST-22B">22b</A> Naidu BN. West FG. Tetrahedron  1997,  53:  16565 

<A NAME="RD10704TST-22C">22c</A> Vanecko JA. West FG. Org Lett.  2002,  4:  2813 

<A NAME="RD10704TST-23">23</A>

With salt [3][Δ-TRISPHAT], no enantioselectivity was expected as no stereoselective induction happens upon ion pairing.¹²