Enantioselective Intramolecular Copper-Catalyzed Aziridination of Sulfamates

Abstract

Intramolecular copper-catalyzed aziridination of sulfamates occurs in very good yields of up to 86% and in up to 84% ee in the presence of (4S,4′S)-2,2′-(propane-2,2-diyl)bis(4-tert-butyl-4,5-dihydro-1,3-oxazole). The resulting aziridines undergo smooth ring opening with different types of nucleophiles in an S_N2-type process.

aziridine - nitrene - copper - asymmetric catalysis - ring opening

References

For representative overviews of aziridine chemistry, see:

<A NAME="RC00207SS-1A">1a</A> Tanner D. Angew. Chem., Int. Ed. Engl.  1994,  33:  599 

<A NAME="RC00207SS-1B">1b</A> Zwanenburg B. ten Holte P. Top. Curr. Chem.  2001,  216:  94 

<A NAME="RC00207SS-1C">1c</A> Sweeney JB. Chem. Soc. Rev.  2002,  31:  247 

<A NAME="RC00207SS-1D">1d</A> Aziridines and Epoxides in Organic Synthesis   Yudin AK. Wiley-VCH; Weinheim: 2006. 

For reviews on aziridine ring opening, see:

<A NAME="RC00207SS-2A">2a</A> Stamm H. J. Prakt. Chem.  1999,  341:  319 

<A NAME="RC00207SS-2B">2b</A> McCoull W. Davis FA. Synthesis  2000,  1347 

<A NAME="RC00207SS-2C">2c</A> Hu XE. Tetrahedron  2004,  60:  2701 

For reviews on the preparation of aziridines, see:

<A NAME="RC00207SS-3A">3a</A> Osborn HMI. Sweeney J. Tetrahedron: Asymmetry  1997,  8:  1693 

<A NAME="RC00207SS-3B">3b</A> Atkinson RS. Tetrahedron  1999,  55:  1519 

<A NAME="RC00207SS-4A">4a</A> Dauban P. Dodd RH. Synlett  2003,  1571 

<A NAME="RC00207SS-4B">4b</A> Müller P. Fruit C. Chem. Rev.  2003,  103:  2905 

<A NAME="RC00207SS-4C">4c</A> Halfen JA. Curr. Org. Chem.  2005,  9:  657 

<A NAME="RC00207SS-4D">4d</A> Katsuki T. Chem. Lett.  2005,  34:  1304 

<A NAME="RC00207SS-4E">4e</A> Espino CG. Du Bois J. In Modern Rhodium-Catalyzed Organic Reactions   Evans P. A. Wiley-VCH; Weinheim: 2006.  p.379 

<A NAME="RC00207SS-4F">4f</A> Watson IDG. Yu L. Yudin AK. Acc. Chem. Res.  2006,  39:  194 

<A NAME="RC00207SS-4G">4g</A> Lebel H. Leogane O. Huard K. Lectard S. Pure Appl. Chem.  2006,  78:  363 

<A NAME="RC00207SS-4H">4h</A> Li Z. He C. Eur. J. Org. Chem.  2006,  4313 

<A NAME="RC00207SS-5A">5a</A> Abramovitch RA. Bailey TD. Takaya T. Uma V. J. Org. Chem.  1974,  39:  340 

<A NAME="RC00207SS-5B">5b</A> Yamada Y. Yamamoto T. Okawara M. Chem. Lett.  1975,  361 

For some representative examples, see:

<A NAME="RC00207SS-6A">6a</A> Evans DA. Faul MM. Bilodeau MT. J. Am. Chem. Soc.  1994,  116:  2742 

<A NAME="RC00207SS-6B">6b</A> Södergren MJ. Alonso DA. Bedekar AV. Andersson PG. Tetrahedron Lett.  1997,  38:  6897 

<A NAME="RC00207SS-6C">6c</A> Dauban P. Dodd RH. J. Org. Chem.  1999,  64:  5304 

<A NAME="RC00207SS-6D">6d</A> Kwong H.-L. Liu D. Chan K.-Y. Lee C.-S. Huang K.-H. Che C.-M. Tetrahedron Lett.  2004,  45:  3965 

<A NAME="RC00207SS-6E">6e</A> Han H. Bae I. Yoo EJ. Lee J. Do Y. Chang S. Org. Lett.  2004,  6:  4109 

<A NAME="RC00207SS-6F">6f</A> Mohr F. Binfield SA. Fettinger JC. Vedernikov AN. J. Org. Chem.  2005,  70:  4833 

For representative examples, see:

<A NAME="RC00207SS-7A">7a</A> Müller P. Baud C. Jacquier Y. Tetrahedron  1996,  52:  1543 

<A NAME="RC00207SS-7B">7b</A> Guthikonda K. Du Bois J. J. Am. Chem. Soc.  2002,  124:  13672 

<A NAME="RC00207SS-7C">7c</A> Liang J.-L. Yuan S.-X. Hong Chan PW. Che C.-M. Org. Lett.  2002,  4:  4507 

<A NAME="RC00207SS-7D">7d</A> Padwa A. Flick AC. Leverett CA. Stengel T. J. Org. Chem.  2004,  69:  6377 

<A NAME="RC00207SS-7E">7e</A> Keaney GF. Wood JL. Tetrahedron Lett.  2005,  46:  4031 

<A NAME="RC00207SS-7F">7f</A> Catino AJ. Nichols JM. Forslund RE. Doyle MP. Org. Lett.  2005,  7:  2787 

<A NAME="RC00207SS-7G">7g</A> Hayes CJ. Beavis PW. Humphries LA. Chem. Commun.  2006,  4501 

For recent examples, see:

<A NAME="RC00207SS-8A">8a</A> Davies HML. Long MS. Angew. Chem. Int. Ed.  2005,  44:  3518 

<A NAME="RC00207SS-8B">8b</A> Liang C. Robert-Peillard F. Fruit C. Müller P. Dodd RH. Dauban P. Angew. Chem. Int. Ed.  2006,  45:  4641 

<A NAME="RC00207SS-8C">8c</A> Fiori KW. Du Bois J. J. Am. Chem. Soc.  2007,  129:  562 

For recent examples, see:

<A NAME="RC00207SS-9A">9a</A> White RD. Keaney GF. Slown CD. Wood JL. Org. Lett.  2004,  6:  1123 

<A NAME="RC00207SS-9B">9b</A> Provoost OY. Hedley SJ. Hazelwood AJ. Harrity JPA. Tetrahedron Lett.  2006,  47:  331 

<A NAME="RC00207SS-9C">9c</A> Trost BM. Dong G. J. Am. Chem. Soc.  2006,  128:  6054 

<A NAME="RC00207SS-9D">9d</A> Kessler A. Faure H. Petrel C. Rognan D. Césario M. Ruat M. Dauban P. Dodd RH. J. Med. Chem.  2006,  49:  5119 

Rhodium-catalyzed nitrene transfer has found application in total synthesis in the field of C-H amination. Impressive examples of syntheses of highly complex natural products are reported in the following articles:

<A NAME="RC00207SS-10A">10a</A> Hinman A. Du Bois J. J. Am. Chem. Soc.  2003,  125:  11510 

<A NAME="RC00207SS-10B">10b</A> Fleming JJ. Du Bois J. J. Am. Chem. Soc.  2006,  128:  3926 

<A NAME="RC00207SS-11A">11a</A> Li Z. Conser KR. Jacobsen EN. J. Am. Chem. Soc.  1993,  115:  5326 

<A NAME="RC00207SS-11B">11b</A> Evans DA. Faul MM. Bilodeau MT. Anderson BA. Barnes DM. J. Am. Chem. Soc.  1993,  115:  5328 

<A NAME="RC00207SS-11C">11c</A> Sanders CJ. Gillespie KM. Bell D. Scott P. J. Am. Chem. Soc.  2000,  122:  7132 

<A NAME="RC00207SS-11D">11d</A> Gillespie KM. Sanders CJ. O’Shaughnessy P. Westmoreland I. Thickitt CP. Scott P. J. Org. Chem.  2002,  67:  3450 

<A NAME="RC00207SS-11E">11e</A> Ryan D. McMorn P. Bethell D. Hutchings G. Org. Biomol. Chem.  2004,  2:  3566 

<A NAME="RC00207SS-11F">11f</A> Xu J. Ma L. Jiao P. Chem. Commun.  2004,  1616 

<A NAME="RC00207SS-11G">11g</A> Ma L. Du D.-M. Xu J. J. Org. Chem.  2005,  70:  10155 

<A NAME="RC00207SS-11H">11h</A> Wang X. Ding K. Chem. Eur. J.  2006,  12:  4568 

<A NAME="RC00207SS-12A">12a</A> Yu XQ. Huang J.-S. Zhou X.-G. Che C.-M. Org. Lett.  2000,  2:  2233 

<A NAME="RC00207SS-12B">12b</A> Espino CG. Du Bois J. Angew. Chem. Int. Ed.  2001,  40:  598 

<A NAME="RC00207SS-12C">12c</A> Dauban P. Sanière L. Tarrade A. Dodd RH. J. Am. Chem. Soc.  2001,  123:  7707 

<A NAME="RC00207SS-13A">13a</A> Espino CG. Wehn PM. Chow J. Du Bois J. J. Am. Chem. Soc.  2001,  123:  6935 

<A NAME="RC00207SS-13B">13b</A> Wehn PM. Lee J. Du Bois J. Org. Lett.  2003,  5:  4823 

<A NAME="RC00207SS-13C">13c</A> Fruit C. Müller P. Tetrahedron: Asymmetry  2004,  15:  1019 

<A NAME="RC00207SS-13D">13d</A> Liang J.-L. Yuan S.-X. Huang J.-S. Che C.-M. J. Org. Chem.  2004,  69:  3610 

<A NAME="RC00207SS-13E">13e</A> Cui Y. He C. Angew. Chem. Int. Ed.  2004,  43:  4210 

<A NAME="RC00207SS-13F">13f</A> Guthikonda K. Wehn PM. Caliando BJ. Du Bois J. Tetrahedron  2006,  62:  11331 

<A NAME="RC00207SS-14">14</A> Duran F. Leman L. Ghini A. Burton G. Dauban P. Dodd RH. Org. Lett.  2002,  4:  2481 

<A NAME="RC00207SS-15">15</A> Okada M. Iwashita S. Koizumi N. Tetrahedron Lett.  2000,  41:  7047 

<A NAME="RC00207SS-16">16</A>

At this stage of the experimental work, preliminary investigations of the nucleophilic ring opening of aziridine 4a with benzylamine revealed that it occurs without loss of stereochemical information. No trace of the cis-isomer of the aziridine ring-opened product was observed, while the ee of the latter matched the ee of the aziridine 4a. According to subsequent experiments (vide infra) and Du Bois’s work (see ref. 13f), the reaction is believed to occur by an S_N2 process. This result was used to derivatize aziridines 4b-j by reaction with benzylamine in order to determine the enantioselectivity of the asymmetric intramolecular aziridination of sulfamates 2b-j.

<A NAME="RC00207SS-17A">17a</A> Li Z. Quan RW. Jacobsen EN. J. Am. Chem. Soc.  1995,  117:  5889 

<A NAME="RC00207SS-17B">17b</A> Brandt P. Södergren MJ. Andersson PG. Norrby P.-O. J. Am. Chem. Soc.  2000,  122:  8013 

<A NAME="RC00207SS-18">18</A> For the diastereoselective catalytic aziridination of acrylate derivatives, see: Di Chenna PH. Robert-Peillard F. Dauban P. Dodd RH. Org. Lett.  2004,  6:  4503 

<A NAME="RC00207SS-19">19</A>

Estéoule, A.; Dodd, R. H.; Dauban, P. unpublished results.

<A NAME="RC00207SS-20">20</A> For a review on cyclic sulfamidates, see: Meléndez RE. Lubell WD. Tetrahedron  2003,  59:  2581 

<A NAME="RC00207SS-21">21</A>

‘Collect’ data collection software; Nonius, B. V.; 1999.

<A NAME="RC00207SS-22">22</A> PLATON, A Multipurpose Crystallographic Tool   Spek AL. Utrecht University; Utrecht, The Netherlands: 2007. 

<A NAME="RC00207SS-23">23</A> Otwinowski Z. Minor W. In Methods in Enzymology. Macromolecular Crystallography   Part A, Vol. 276:  Carter CW. Sweet RM. Academic Press; New York: 1997.  p.307 

<A NAME="RC00207SS-24">24</A> Sheldrick GM. SHELX97, Program for the Refinement of Crystal Structures from Diffraction Data   University of Göttingen; Göttingen, Germany: 1997.