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.

Key words

aziridine - nitrene - copper - asymmetric catalysis - ring opening

References

• For representative overviews of aziridine chemistry, see:
• 1a Tanner D. Angew. Chem., Int. Ed. Engl.  1994,  33:  599 
• 1b Zwanenburg B. ten Holte P. Top. Curr. Chem.  2001,  216:  94 
• 1c Sweeney JB. Chem. Soc. Rev.  2002,  31:  247 
• 1d Aziridines and Epoxides in Organic Synthesis   Yudin AK. Wiley-VCH; Weinheim: 2006. 
• For reviews on aziridine ring opening, see:
• 2a Stamm H. J. Prakt. Chem.  1999,  341:  319 
• 2b McCoull W. Davis FA. Synthesis  2000,  1347 
• 2c Hu XE. Tetrahedron  2004,  60:  2701 
• For reviews on the preparation of aziridines, see:
• 3a Osborn HMI. Sweeney J. Tetrahedron: Asymmetry  1997,  8:  1693 
• 3b Atkinson RS. Tetrahedron  1999,  55:  1519 
• 4a Dauban P. Dodd RH. Synlett  2003,  1571 
• 4b Müller P. Fruit C. Chem. Rev.  2003,  103:  2905 
• 4c Halfen JA. Curr. Org. Chem.  2005,  9:  657 
• 4d Katsuki T. Chem. Lett.  2005,  34:  1304 
• 4e Espino CG. Du Bois J. In Modern Rhodium-Catalyzed Organic Reactions   Evans P. A. Wiley-VCH; Weinheim: 2006.  p.379 
• 4f Watson IDG. Yu L. Yudin AK. Acc. Chem. Res.  2006,  39:  194 
• 4g Lebel H. Leogane O. Huard K. Lectard S. Pure Appl. Chem.  2006,  78:  363 
• 4h Li Z. He C. Eur. J. Org. Chem.  2006,  4313 
• 5a Abramovitch RA. Bailey TD. Takaya T. Uma V. J. Org. Chem.  1974,  39:  340 
• 5b Yamada Y. Yamamoto T. Okawara M. Chem. Lett.  1975,  361 
• For some representative examples, see:
• 6a Evans DA. Faul MM. Bilodeau MT. J. Am. Chem. Soc.  1994,  116:  2742 
• 6b Södergren MJ. Alonso DA. Bedekar AV. Andersson PG. Tetrahedron Lett.  1997,  38:  6897 
• 6c Dauban P. Dodd RH. J. Org. Chem.  1999,  64:  5304 
• 6d Kwong H.-L. Liu D. Chan K.-Y. Lee C.-S. Huang K.-H. Che C.-M. Tetrahedron Lett.  2004,  45:  3965 
• 6e Han H. Bae I. Yoo EJ. Lee J. Do Y. Chang S. Org. Lett.  2004,  6:  4109 
• 6f Mohr F. Binfield SA. Fettinger JC. Vedernikov AN. J. Org. Chem.  2005,  70:  4833 
• For representative examples, see:
• 7a Müller P. Baud C. Jacquier Y. Tetrahedron  1996,  52:  1543 
• 7b Guthikonda K. Du Bois J. J. Am. Chem. Soc.  2002,  124:  13672 
• 7c Liang J.-L. Yuan S.-X. Hong Chan PW. Che C.-M. Org. Lett.  2002,  4:  4507 
• 7d Padwa A. Flick AC. Leverett CA. Stengel T. J. Org. Chem.  2004,  69:  6377 
• 7e Keaney GF. Wood JL. Tetrahedron Lett.  2005,  46:  4031 
• 7f Catino AJ. Nichols JM. Forslund RE. Doyle MP. Org. Lett.  2005,  7:  2787 
• 7g Hayes CJ. Beavis PW. Humphries LA. Chem. Commun.  2006,  4501 
• For recent examples, see:
• 8a Davies HML. Long MS. Angew. Chem. Int. Ed.  2005,  44:  3518 
• 8b Liang C. Robert-Peillard F. Fruit C. Müller P. Dodd RH. Dauban P. Angew. Chem. Int. Ed.  2006,  45:  4641 
• 8c Fiori KW. Du Bois J. J. Am. Chem. Soc.  2007,  129:  562 
• For recent examples, see:
• 9a White RD. Keaney GF. Slown CD. Wood JL. Org. Lett.  2004,  6:  1123 
• 9b Provoost OY. Hedley SJ. Hazelwood AJ. Harrity JPA. Tetrahedron Lett.  2006,  47:  331 
• 9c Trost BM. Dong G. J. Am. Chem. Soc.  2006,  128:  6054 
• 9d 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:
• 10a Hinman A. Du Bois J. J. Am. Chem. Soc.  2003,  125:  11510 
• 10b Fleming JJ. Du Bois J. J. Am. Chem. Soc.  2006,  128:  3926 
• 11a Li Z. Conser KR. Jacobsen EN. J. Am. Chem. Soc.  1993,  115:  5326 
• 11b Evans DA. Faul MM. Bilodeau MT. Anderson BA. Barnes DM. J. Am. Chem. Soc.  1993,  115:  5328 
• 11c Sanders CJ. Gillespie KM. Bell D. Scott P. J. Am. Chem. Soc.  2000,  122:  7132 
• 11d Gillespie KM. Sanders CJ. O’Shaughnessy P. Westmoreland I. Thickitt CP. Scott P. J. Org. Chem.  2002,  67:  3450 
• 11e Ryan D. McMorn P. Bethell D. Hutchings G. Org. Biomol. Chem.  2004,  2:  3566 
• 11f Xu J. Ma L. Jiao P. Chem. Commun.  2004,  1616 
• 11g Ma L. Du D.-M. Xu J. J. Org. Chem.  2005,  70:  10155 
• 11h Wang X. Ding K. Chem. Eur. J.  2006,  12:  4568 
• 12a Yu XQ. Huang J.-S. Zhou X.-G. Che C.-M. Org. Lett.  2000,  2:  2233 
• 12b Espino CG. Du Bois J. Angew. Chem. Int. Ed.  2001,  40:  598 
• 12c Dauban P. Sanière L. Tarrade A. Dodd RH. J. Am. Chem. Soc.  2001,  123:  7707 
• 13a Espino CG. Wehn PM. Chow J. Du Bois J. J. Am. Chem. Soc.  2001,  123:  6935 
• 13b Wehn PM. Lee J. Du Bois J. Org. Lett.  2003,  5:  4823 
• 13c Fruit C. Müller P. Tetrahedron: Asymmetry  2004,  15:  1019 
• 13d Liang J.-L. Yuan S.-X. Huang J.-S. Che C.-M. J. Org. Chem.  2004,  69:  3610 
• 13e Cui Y. He C. Angew. Chem. Int. Ed.  2004,  43:  4210 
• 13f Guthikonda K. Wehn PM. Caliando BJ. Du Bois J. Tetrahedron  2006,  62:  11331 
• 14 Duran F. Leman L. Ghini A. Burton G. Dauban P. Dodd RH. Org. Lett.  2002,  4:  2481 
• 15 Okada M. Iwashita S. Koizumi N. Tetrahedron Lett.  2000,  41:  7047 
• 17a Li Z. Quan RW. Jacobsen EN. J. Am. Chem. Soc.  1995,  117:  5889 
• 17b Brandt P. Södergren MJ. Andersson PG. Norrby P.-O. J. Am. Chem. Soc.  2000,  122:  8013 
• 18 For the diastereoselective catalytic aziridination of acrylate derivatives, see: Di Chenna PH. Robert-Peillard F. Dauban P. Dodd RH. Org. Lett.  2004,  6:  4503 
• 20 For a review on cyclic sulfamidates, see: Meléndez RE. Lubell WD. Tetrahedron  2003,  59:  2581 
• 22 PLATON, A Multipurpose Crystallographic Tool   Spek AL. Utrecht University; Utrecht, The Netherlands: 2007. 
• 23 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 
• 24 Sheldrick GM. SHELX97, Program for the Refinement of Crystal Structures from Diffraction Data   University of Göttingen; Göttingen, Germany: 1997. 

16

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.

19

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

21

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