Highly Symmetrical Amino Acid-Derived N,N′-Diacylated Sulfodiimines

Abstract

A mild and efficient method for the coupling of sulfodiimines with N-protected amino acids has been developed, yielding the corresponding N,N′-diacylated sulfodiimines with up to 94% yield.

coupling - amino acids - acylations - peptides - sulfodiimines - asymmetric synthesis

References

Reviews:

<A NAME="RZ23504SS-1A">1a</A> Reggelin M. Zur C. Synthesis  2000,  1 

<A NAME="RZ23504SS-1B">1b</A> Mikolajczk M. Drabowicz J. Kielbasinski P. Chiral Sulfur Reagents   CRC Press; Boca Raton: 1997. 

<A NAME="RZ23504SS-1C">1c</A> Pyne S. Sulfur Reports  1992,  12:  57 

<A NAME="RZ23504SS-1D">1d</A> Haake M. In Houben-Weyl, Methoden der organischen Chemie   Vol. E11:  Klamann D. Thieme; Stuttgart: 1985.  p.1299 

<A NAME="RZ23504SS-1E">1e</A> Johnson CR. Acc. Chem. Res.  1973,  6:  341 

<A NAME="RZ23504SS-1F">1f</A> Johnson CR. Aldrichimica Acta  1985,  18:  3 

For some recent examples stemming from this group, see:

<A NAME="RZ23504SS-2A">2a</A> Bolm C. Müller D. Dalhoff C. Hackenberger CPR. Weinhold E. Bioorg. Med. Chem. Lett.  2003,  13:  3207 

<A NAME="RZ23504SS-2B">2b</A> Bolm C. Müller D. Hackenberger CPR. Org. Lett.  2002,  4:  893 

<A NAME="RZ23504SS-2C">2c</A> Bolm C. Moll G. Kahmann JD. Chem.-Eur. J.  2001,  7:  1118 

<A NAME="RZ23504SS-3">3</A> Okamura H. Bolm C. Chem. Lett.  2004,  33:  482 

For recent examples, see:

<A NAME="RZ23504SS-4A">4a</A> Langner M. Bolm C. Angew. Chem. Int. Ed.  2004,  43:  5984 

<A NAME="RZ23504SS-4B">4b</A> Bolm C. Martin M. Simic O. Verrucci M. Org. Lett.  2003,  5:  427 

<A NAME="RZ23504SS-4C">4c</A> Bolm C. Verrucci M. Simic O. Cozzi PG. Raabe G. Okamura H. Chem. Commun.  2003,  2816 

<A NAME="RZ23504SS-4D">4d</A> Bolm C. Simic O. J. Am. Chem. Soc.  2001,  123:  3830 

<A NAME="RZ23504SS-4E">4e</A> Bolm C. Simic O. Martin M. Synlett  2001,  1878 

<A NAME="RZ23504SS-4F">4f</A> Harmata M. Ghosh SK. Org. Lett.  2001,  3:  3321 

<A NAME="RZ23504SS-4G">4g</A> See also: Bolm C. Martin M. Gescheidt G. Palivan C. Neshchadin D. Bertagnolli H. Feth M. Schweiger A. Mitrikas G. Harmer J. J. Am. Chem. Soc.  2003,  125:  6222 

<A NAME="RZ23504SS-5">5</A> Harmata M. Chemtracts: Org. Chem.  2003,  16:  660 

<A NAME="RZ23504SS-6">6</A> Review: Haake M. In Topics in Sulfur Chemistry   Senning A. Thieme; Stuttgart: 1976.  Vol. 1. p.185 

<A NAME="RZ23504SS-7">7</A> Diederich WE. Haake M. J. Org. Chem.  2003,  68:  3817 ; and references therein

<A NAME="RZ23504SS-8">8</A> To the best of our knowledge, there is only one single report on the synthesis of a non-racemic sulfodiimine, and in this case, the enantiomer ratio has not been determined: Christensen BW. Kjær A. J. Chem. Soc., Chem. Commun.  1975,  784 

<A NAME="RZ23504SS-9">9</A> Haake M. Fode H. Eichenauer B. Liebigs Ann. Chem.  1972,  759:  107 

<A NAME="RZ23504SS-10">10</A> Hackenberger CPR. Raabe G. Bolm C. Chem.-Eur. J.  2004,  10:  2942 ; and references therein

For reviews on coupling reagents, see:

<A NAME="RZ23504SS-11A">11a</A> Han S.-Y. Kim Y.-A. Tetrahedron  2004,  60:  2447 

<A NAME="RZ23504SS-11B">11b</A> Klausner YS. Bodansky M. Synthesis  1972,  453 

<A NAME="RZ23504SS-12">12</A>

In this case, the meso-product resulting from an epimerization would possess two diastereotopic methyl groups. Those would be in rather different chemical and electronic environments and, therefore, two different chemical shifts would be likely to occur in the ¹H NMR spectrum.