Abstract
N -Alkylated sulfoximines have been synthesized in good yields by acylation of NH -sulfoximines followed by carbonyl reduction with complexed boranes. Enantiopure substrates react without racemization, and stereogenic centers originating from the acylating component are retained. If the acylation is performed by DCC coupling, this two-step procedure represents a rare example of a formal N-alkylation of sulfoximines under base-free conditions.
Keywords
acylation - borane - chirality - reduction - sulfoximine
References and Notes
1a Johnson CR.
Aldrichimica Acta
1985,
18:
3
1b Johnson CR.
Acc. Chem. Res.
1973,
6:
341
1c Johnson CR. In Comprehensive Organic Chemistry
Vol. 3:
Barton D.
Ollis WD.
Pergamon Press;
Oxford:
1979.
p.223
1d Pyne SG.
Sulfur Rep.
1992,
12:
57
1e Reggelin M.
Zur C.
Synthesis
2000,
1
2a Pyne SG.
Dong Z.
Skelton BW.
White AH.
J. Org. Chem.
1997,
62:
2337
2b Reggelin M.
Heinrich T.
Angew. Chem. Int. Ed.
1998,
37:
2883 ; Angew. Chem . 1998 , 110 , 3005
2c Bosshammer S.
Gais H.-J.
Synthesis
1998,
919
2d Hachtel J.
Gais H.-J.
Eur. J. Org. Chem.
2000,
1457
2e Gais H.-J.
Loo R.
Das P.
Raabe G.
Tetrahedron Lett.
2000,
41:
2851
2f Paquette LA.
Gao Z.
Ni Z.
Smith GF.
J. Am. Chem. Soc.
1998,
120:
2543
2g Harmata M.
Kahraman M.
Jones DE.
Pavri N.
Weatherwax SE.
Tetrahedron
1998,
54:
9995
2h Harmata M.
Pavri N.
Angew. Chem. Int. Ed.
1999,
38:
2419 ; Angew. Chem . 1999 , 111 , 2577
2i Bolm C.
Muñiz K.
Aguilar N.
Kesselgruber M.
Raabe G.
Synthesis
1999,
1251
2j Bolm C.
Kesselgruber M.
Muñiz K.
Raabe G.
Organometallics
2000,
19:
1648
3a Bolm C.
Felder M.
Müller J.
Synlett
1992,
439
3b Bolm C.
Felder M.
Tetrahedron Lett.
1993,
34:
6041
3c Bolm C.
Müller J.
Schlingloff G.
Zehnder M.
Neuburger M.
J. Chem. Soc., Chem. Commun.
1993,
182
3d Bolm C.
Seeger A.
Felder M.
Tetrahedron Lett.
1993,
34:
8079
3e Bolm C.
Felder M.
Synlett
1994,
655
3f Bolm C.
Müller P.
Tetrahedron Lett.
1995,
36:
1625
3g Bolm C.
Müller P.
Acta Chem. Scand.
1996,
50:
305
3h Bolm C.
Kaufmann D.
Zehnder M.
Neuburger M.
Tetrahedron Lett.
1996,
37:
3985
3i Bolm C.
Simić O.
J. Am. Chem. Soc.
2001,
123:
3830
3j Harmata M.
Ghosh SK.
Org. Lett.
2001,
3:
3321
4a Bolm C.
Kahmann JD.
Moll G.
Tetrahedron Lett.
1997,
38:
1169
4b Bolm C.
Moll G.
Kahmann JD.
Chem.-Eur. J.
2001,
7:
1118
4c Bolm C.
Müller D.
Hackenberger CPR.
Org. Lett.
2002,
4:
893
5a Fusco R.
Tericoni F.
Chim. Ind.
1965,
47:
61
5b Johnson CR.
Schroeck CW.
J. Am. Chem. Soc.
1973,
95:
7418
5c Shiner CS.
Berks AH.
J. Org. Chem.
1988,
53:
5542
5d Mori K.
Toda F.
Chem. Lett.
1988,
1997
5e Brandt J.
Gais H.-J.
Tetrahedron: Asymmetry
1997,
6:
909
6a Tamura Y.
Sumoto K.
Minamikawa J.
Ikeda M.
Tetrahedron Lett.
1972,
37:
4137
6b Johnson CR.
Kirchhoff RA.
Corkins HG.
J. Org. Chem.
1974,
39:
2458
6c Müller JFK.
Vogt P.
Tetrahedron Lett.
1998,
39:
4805
6d Bach T.
Körber C.
Eur. J. Org. Chem.
1999,
1033
6e Lacote E.
Amatore M.
Fensterbank L.
Malacria M.
Synlett
2002,
116
7a Kagan HB.
Diter P. In Organosulfur Chemistry
Vol. 2:
Page PCB.
Academic Press;
New York:
1998.
p.1
7b Kagan HB.
Luukas T. In Transition Metals for Organic Synthesis
Vol. 2:
Beller M.
Bolm C.
Wiley-VCH;
Weinheim:
1998.
p.361
7c Kagan HB. In Catalytic Asymmetric Synthesis
2nd Ed.:
Ojima I.
VCH Publisher;
New York:
2000.
p.327
7d Bolm C.
Muñiz K. In Comprehensive Asymmetric Catalysis
Jacobsen EN.
Pfaltz A.
Yamamoto H.
Springer Verlag;
Berlin:
1999.
p.697
8a Andersen KK.
Tetrahedron Lett.
1962,
3:
93
8b Andersen KK.
J. Org. Chem.
1964,
29:
1952
8c Solladié G.
Hutt J.
Girardin A.
Synthesis
1987,
173
8d Fernandez I.
Khiar N.
Llera JM.
Alcudia F.
J. Org. Chem.
1992,
57:
6789
8e Fernandez I.
Llera JM.
Alcudia F.
Tetrahedron Lett.
1991,
32:
7299
8f Guerrero-de la Rosa V.
Ordonez M.
Llera JM.
Alcudia F.
Synthesis
1995,
761
8g Capozzi MAM.
Cardellicchio C.
Naso F.
Tortorella P.
J. Org. Chem.
2001,
66:
5933
9a Williams TR.
Booms RE.
Cram DJ.
J. Am. Chem. Soc.
1971,
93:
7338
9b Schmidbaur H.
Kammer G.
Chem. Ber.
1971,
104:
3234
9c Johnson CR.
Schroeck CW.
Shanklin JR.
J. Am. Chem. Soc.
1973,
95:
7424
N -Methyl and N -ethyl sulfoximines can also be obtained by alkylations with trialkyloxonium salts:
10a Johnson CR.
Rigan JJ.
Haake M.
McCants D.
Keiser JE.
Gertsema A.
Tetrahedron Lett.
1968,
3719
10b Johnson CR.
Haake M.
Schroeck CW.
J. Am. Chem. Soc.
1970,
92:
6594
11a Bolm C.
Hildebrand JP.
Tetrahedron Lett.
1998,
39:
5731
11b Bolm C.
Hildebrand JP.
J. Org. Chem.
2000,
65:
169
11c Bolm C.
Hildebrand JP.
Rudolph J.
Synthesis
2000,
911
12 Johnson CR.
Lavergne OM.
J. Org. Chem.
1993,
58:
1922
13 Bordwell FG.
Brance JC.
Johnson CR.
Vanier NR.
J. Org. Chem.
1980,
45:
3884
14 N -trifluoromethanesulfonations of sulfoximines see: Craig D.
Geach NJ.
Synlett
1993,
481
15 Brown HC.
Heim P.
J. Org. Chem.
1973,
38:
912
16 Both enantiomers of S -methyl-S- phenyl-sulfoximine (1a ) are commercially available (Lancaster). To prepare 1a on a large scale we recommend the improved protocol described in ref.
[5e
17 The reaction was monitored by TLC after 4, 8, 16 and 36 hours and quenched when the product formation was complete.
18 Bolm C.
Bienewald F.
Harms H.
Synlett
1996,
775
19 Bolm C.
Simić O.
Martin M.
Synlett
2001,
1878
20 For a discussion on this analogy see ref.
[18
21 The sulfoximines mentioned in entries 2 and 3 of Table
[2 S )-S -methyl-S- phenyl-sulfoximine by metalation/alkylation sequence. Those shown in entries 4-8 (Table
[2 6
22 N -β-Aminoalkylated diarylsulfoximines have been shown for example to be spasmolytically highly active compounds. Satzinger G.
Stoss P.
Arzneim.-Forsch.
1970,
20:
1214
