A Convenient and Scaleable Synthesis of 11,12-Diamino-9,10-dihydro-9,10-ethanoanthracene and Its Enantiomers

Abstract

A convenient synthesis of 11,12-diamino-9,10-dihydro-9,10-ethanoanthracene (1) is described. A Diels-Alder reaction between fumaryl chloride and anthracene provides an acid chloride. Conversion into an acyl azide followed by a thermal Curtius rearrangement and saponification affords the racemic diamine. Diastereoisomeric salt resolution provides the single enantiomer products, which are used as the chiral backbone of several ligands in asymmetric catalysis, including the Trost asymmetric allylic alkylation ligand 2.

asymmetric catalysis - resolution - Diels-Alder reaction - palladium - allylic alkylation

References

<A NAME="RC06105SS-1">1</A>

Current address: Bayer Cropscience AG, Industriepark Höchst, D-65926, Frankfurt, Germany.

<A NAME="RC06105SS-2A">2a</A> Blaser HU. Chem. Commun.  2003,  293 

<A NAME="RC06105SS-2B">2b</A> Lennon IC. Pilkington CJ. Synthesis  2003,  1639 

<A NAME="RC06105SS-3A">3a</A> Trost BM. Van Vranken DL. Bingel C. J. Am. Chem. Soc.  1992,  114:  9327 

<A NAME="RC06105SS-3B">3b</A> Trost BM. Van Vranken DL. Angew. Chem., Int. Ed. Engl.  1992,  31:  228 

<A NAME="RC06105SS-3C">3c</A> Trost BM. Crawley ML. Chem. Rev.  2003,  103:  2921 

<A NAME="RC06105SS-4A">4a</A> Trost BM. Toste FD. J. Am. Chem. Soc.  1998,  120:  9074 

<A NAME="RC06105SS-4B">4b</A> Fox ME. Lennon IC. Meek G. Tetrahedron Lett.  2002,  43:  2899 

<A NAME="RC06105SS-5A">5a</A> Trost BM. Schroeder GM. Kristensen J. Angew. Chem. Int. Ed.  2002,  41:  3492 

<A NAME="RC06105SS-5B">5b</A> Trost BM. Tang W. J. Am. Chem. Soc.  2003,  125:  8744 

<A NAME="RC06105SS-5C">5c</A> Trost BM. Xu J. J. Am. Chem. Soc.  2005,  127:  2846 

<A NAME="RC06105SS-6">6</A> Trost BM. Frederiksen MU. Angew. Chem. Int. Ed.  2005,  44:  308 

<A NAME="RC06105SS-7A">7a</A> Trost BM. Breit B. Peukert S. Zambrano J. Ziller JW. Angew. Chem., Int. Ed. Engl.  1995,  34:  2386 

<A NAME="RC06105SS-7B">7b</A> Trost BM. Madsen R. Guile SG. Elia AEH. Angew. Chem., Int. Ed. Engl.  1996,  35:  1569 

<A NAME="RC06105SS-7C">7c</A> Trost BM. Kallander LS. J. Org. Chem.  1999,  64:  5427 

<A NAME="RC06105SS-8">8</A> Cobley CJ. Henschke JP. Adv. Synth. Catal.  2003,  345:  195 

<A NAME="RC06105SS-9">9</A> Maier NM. Uray G. J. Chromatogr. A  1996,  740:  11 

<A NAME="RC06105SS-10">10</A> Allenmark S. Skogsberg U. Thunberg L. Tetrahedron: Asymmetry  2000,  11:  3527 

<A NAME="RC06105SS-11">11</A> Thunberg L. Allenmark S. J. Chromatogr. A  2004,  1026:  65 

<A NAME="RC06105SS-12">12</A> Wang B. Feng X. Huang Y. Liu H. Cui X. Jiang Y. J. Org. Chem.  2002,  67:  2175 

<A NAME="RC06105SS-13">13</A> Verboom RC. Plietker BJ. Bäckvall JE. J. Organomet. Chem.  2003,  687:  508 

<A NAME="RC06105SS-14">14</A> Belokon YN. Fuentes J. North M. Steed JW. Tetrahedron  2004,  60:  3191 

<A NAME="RC06105SS-15">15</A> Bachmann WE. Scott LB. J. Am. Chem. Soc.  1948,  70:  1458 

<A NAME="RC06105SS-16">16</A> Brienen M.-J. Jacques J. Bull. Soc. Chim. Fr.  1973,  190 

<A NAME="RC06105SS-17">17</A> Hagishita S. Kuriyama K. Tetrahedron  1972,  28:  1435 

<A NAME="RC06105SS-18">18</A> Example of fumaryl chloride being used as a dienophile in Diels-Alder reactions: Jennings-White CLD. Holmes AB. Raithby PR. J. Chem. Soc., Chem. Commun.  1979,  542 

<A NAME="RC06105SS-19">19</A> Jacques J. Collet A. Wilden SH. Enantiomers, Racemates and Resolutions   Krieger Publishing Company; Malabar, Florida: 1991.  Chap. 5. p.251-368  

<A NAME="RC06105SS-20">20</A> Lennon IC. In Handbook of Reagents for Organic Synthesis. Chiral Reagents for Asymmetric Synthesis   Paquette LA. Wiley; New York: 2003.  p.99