Abstract
Starting from the corresponding sulfides, N-cyano
sulfoximines can easily be accessed under metal-free conditions
via the corresponding N-cyano-substituted
sulfilimines. The reaction sequence involves a sulfide imination
with cyanogen amide in presence of a base and N-bromosuccinimide
(NBS) followed by an m-chloroperoxybenzoic
acid (MCPBA) mediated oxidation of the resulting sulfilimine intermediates.
Key words
halides - metal-free - nitriles - sulfides - sulfilimines - sulfoximines
References
For selected recent examples, see:
<A NAME="RZ17710SS-1A">1a</A>
Walker DP.
Zawistoski MP.
McGlynn MA.
Li J.-C.
Kung DW.
Bonnette PC.
Baumann A.
Buckbinder L.
Houser JA.
Boer J.
Mistry A.
Han S.
Xing L.
Guzman-Perez A.
Bioorg.
Med. Chem. Lett.
2009,
19:
3253
<A NAME="RZ17710SS-1B">1b</A>
García Mancheño O.
Dallimore J.
Plant A.
Bolm C.
Adv. Synth.
Catal.
2010,
352:
309
<A NAME="RZ17710SS-1C">1c</A>
Jeschke P,
Thielert W, and
Hungenberg H. inventors; WO 022897 A2.
(Bayer
CropScience AG)
<A NAME="RZ17710SS-1D">1d</A>
Jautelat R,
Lücking U,
Siemeister G,
Schulze J, and
Lienau P. inventors; (Bayer
Schering Pharma AG) 046035 A1.
For reviews, see:
<A NAME="RZ17710SS-2A">2a</A>
Reggelin M.
Zur C.
Synthesis
2000,
1
<A NAME="RZ17710SS-2B">2b</A>
Harmata M.
Chemtracts
2003,
16:
660
<A NAME="RZ17710SS-2C">2c</A>
Okamura H.
Bolm C.
Chem. Lett.
2004,
33:
482
<A NAME="RZ17710SS-2D">2d</A>
Bentley R.
Chem.
Soc. Rev.
2005,
34:
609
<A NAME="RZ17710SS-2E">2e</A>
Worch C.
Mayer AC.
Bolm C. In Organosulfur Chemistry in Asymmetric Synthesis
Toru T.
Bolm C.
Wiley-VCH;
Weinheim:
2008.
p.209
For recent applications of sulfoximines
as chiral ligands in metal catalysis, see:
<A NAME="RZ17710SS-3A">3a</A>
Frings M.
Atodiresei I.
Wang Y.
Runsink J.
Raabe G.
Bolm C.
Chem. Eur. J.
2010,
16:
4577
<A NAME="RZ17710SS-3B">3b</A>
Frings M.
Goedert D.
Bolm C.
Chem.
Commun.
2010, DOI: 10.1039/C0CC00996B;
and references therein
For Cu catalysis, see:
<A NAME="RZ17710SS-4A">4a</A>
Kwart H.
Kahn AA.
J. Am. Chem. Soc.
1967,
89:
1950
<A NAME="RZ17710SS-4B">4b</A>
Müller JFK.
Vogt P.
Tetrahedron
Lett.
1998,
39:
4805
<A NAME="RZ17710SS-4C">4c</A>
Lacôte E.
Amatore M.
Fensterbank L.
Malacria M.
Synlett
2002,
116
For Rh catalysis, see:
<A NAME="RZ17710SS-4D">4d</A>
Okamura H.
Bolm C.
Org. Lett.
2004,
6:
1305
For Ag catalysis, see:
<A NAME="RZ17710SS-4E">4e</A>
Cho GY.
Bolm C.
Org. Lett.
2005,
7:
4983
For Fe catalysis, see:
<A NAME="RZ17710SS-4F">4f</A>
Bach T.
Körber C.
Tetrahedron Lett.
1998,
39:
5015
<A NAME="RZ17710SS-4G">4g</A>
Bach T.
Körber C.
Eur. J. Org. Chem.
1999,
64:
1033
<A NAME="RZ17710SS-4H">4h</A>
García Mancheño O.
Bolm C.
Org. Lett.
2006,
8:
2349
<A NAME="RZ17710SS-4I">4i</A>
Bolm C.
García Mancheño O.
Chem.
Eur. J.
2007,
13:
6674
<A NAME="RZ17710SS-4J">4j</A>
Bolm C.
García Mancheño O.
Dallimore J.
Plant A.
Org.
Lett.
2009,
11:
2429
For metal-free sulfur iminations,
see:
<A NAME="RZ17710SS-5A">5a</A>
Cho GY.
Bolm C.
Tetrahedron Lett.
2005,
46:
8007
<A NAME="RZ17710SS-5B">5b</A>
Siu T.
Picard CJ.
Yudin AK.
J. Org. Chem.
2005,
70:
932
<A NAME="RZ17710SS-5C">5c</A>
Karabuga S.
Kazaz C.
Kilic H.
Ulukanli S.
Celik A.
Tetrahedron Lett.
2005,
46:
5225
<A NAME="RZ17710SS-5D">5d</A>
Krasnova LB.
Hili RM.
Chernoloz OV.
Yudin AK.
ARKIVOC
2005,
(iv):
26
<A NAME="RZ17710SS-5E">5e</A>
García Mancheño O.
Bolm C.
Org. Lett.
2007,
9:
2951
<A NAME="RZ17710SS-5F">5f</A>
Ochiai M.
Naito M.
Miyamoto K.
Hayashi S.
Nakanishi W.
Chem.
Eur. J.
2010,
in press, DOI: 10.1002/chem.201000759
<A NAME="RZ17710SS-6">6</A>
García Mancheño O.
Bistri O.
Bolm C.
Org.
Lett.
2007,
9:
3809
<A NAME="RZ17710SS-7A">7a</A>
Huang JX,
Rogers RB,
Orr N,
Sparks TC,
Gifford JM,
Loso MR,
Zhu Y, and
Meade T. inventors; (Dow
AgroSciences) WO 149134 A1. Various
N-cyano sulfoximines are of interest as agrochemicals. A prominent
example is the sap-feeding insecticide Sulfoxaflor, which is scheduled
for launch in 2012 by Dow AgroSciences. For details, see:
<A NAME="RZ17710SS-7B">7b</A>
Schade M,
Grimm C,
Faerber M,
Müller K, and
Campbell S. inventors; (Syngenta) WO 040623. For a recent report
on pesticidal combinations containing Sulfoxaflor, see:
For previous syntheses of sulfilimines
and sulfoximines with N-cyano groups,
see:
<A NAME="RZ17710SS-8A">8a</A>
Swern D.
Ikeda I.
Whitfield GF.
Tetrahedron
Lett.
1972,
2635
<A NAME="RZ17710SS-8B">8b</A>
Stoss P.
Satzinger G.
Tetrahedron Lett.
1973,
267
<A NAME="RZ17710SS-8C">8c</A>
Hutchins MGK.
Swern D.
Tetrahedron
Lett.
1981,
22:
4599
<A NAME="RZ17710SS-8D">8d</A>
Kemp JEG.
Ellis D.
Closier MD.
Tetrahedron Lett.
1979,
3781
<A NAME="RZ17710SS-8E">8e</A>
Zhu Y,
Rogers RB, and
Huang JX. inventors; (Dow AgroSciences) US 0228027 A1.
<A NAME="RZ17710SS-9">9</A>
Using I2 instead of NBS
under those conditions led to the desired products in lower yields.
<A NAME="RZ17710SS-10">10</A>
Attempting to use other oxidants such
as KMnO4 for the sulfilimine oxidations led to lower
sulfoximine yields.
