Abstract
The condensation of allenylzinc (±)-1 onto N -tert -butanesulfinimines (±)-2 leads to the corresponding trans -ethynyl N -sulfinylaziridines with an excellent diastereoselection.
Key words
aziridines - asymmetric synthesis - carbenoid - chiral resolution - zinc
References 1 Propargylic Carbenoids, Part 3. For Part 2 see ref. 10a.
2a Padwa A.
Murphree S.
Progress in Heterocyclic Chemistry
2003,
15:
75
2b Atkinson RS.
Tetrahedron
1999,
55:
1519
2c Ibuka T.
Chem. Soc. Rev.
1998,
27:
145
2d Osborn HMI.
Sweeney J.
Tetrahedron: Asymmetry
1997,
8:
1693
2e Rayner CM.
Synlett
1997,
11
2f Tanner D.
Angew. Chem., Int. Ed. Engl.
1994,
33:
599
2g Padwa A.
Woolhouse AD. In Comprehensive Heterocyclic Chemistry
Vol 7:
Katritzky AR.
Rees CW.
Pergamon;
Oxford:
1984.
p.47-97
3 Chemla F.
Ferreira F.
Curr. Org. Chem.
2002,
6:
539
4a Ohno H.
Hamaguchi H.
Tanaka T.
J. Org. Chem.
2001,
66:
1867
4b Ohno H.
Hamaguchi H.
Tanaka T.
Org. Lett.
2000,
2:
2161
4c Ohno H.
Toda A.
Fujii N.
Takemoto Y.
Tanaka T.
Ibuka T.
Tetrahedron
2000,
56:
2811
4d Ohno H.
Toda A.
Miwa Y.
Taga T.
Fujii N.
Ibuka T.
Tetrahedron Lett.
1999,
40:
349
5a Labeish NN.
Porfir’eva YI.
Petrov AA.
Zh. Org. Khim.
1984,
20:
402
5b Anderson DJ.
Gilchrist TL.
Gymer GE.
Rees CW.
J. Chem. Soc., Perkin Trans. 1
1973,
550
6 Florio S.
Troisi L.
Capriati V.
Suppa G.
Eur. J. Org. Chem.
2000,
3793
7a Manisse N.
Chuche J.
J. Am. Chem. Soc.
1977,
99:
1272
7b Manisse N.
Chuche J.
Tetrahedron
1977,
33:
2399
8 Li A.-H.
Zhou Y.-G.
Dai L.-X.
Hou X.-L.
Xia L.-J.
Lin L.
Angew. Chem., Int. Ed. Engl.
1997,
36:
1317
9a Ohno H.
Ando K.
Hamaguchi H.
Takeoka Y.
Tanaka T.
J. Am. Chem. Soc.
2002,
124:
15255
9b Ohno H.
Hamaguchi H.
Tanaka T.
Org. Lett.
2001,
3:
2269
9c Ohno H.
Toda A.
Takemoto Y.
Fujii N.
Ibuka T.
J. Chem. Soc., Perkin Trans. 1
1999,
2949
9d Ohno H.
Toda A.
Fujii N.
Ibuka T.
Tetrahedron: Asymmetry
1998,
9:
3929
10a Chemla F.
Ferreira F.
Hebbe V.
Stercklen E.
Eur. J. Org. Chem.
2002,
1385
10b Chemla F.
Hebbe V.
Normant JF.
Tetrahedron Lett.
1999,
40:
8093
11 Netscher T.
Prinzbach H.
Synthesis
1987,
683
12 Cogan DA.
Liu G.
Kim K.
Backes BJ.
Ellman JA.
J. Am. Chem. Soc.
1998,
120:
8011
13
Typical Procedure for the Synthesis of Ethynyl
N
-Sulfinylaziridines (±)-3: To a 0.1 M etheral solution of 3-chloro-1-trimethylsilylpropyne (1.0 equiv) under nitrogen atmosphere TMEDA (1.0 equiv) and n- BuLi (2.2 M in hexanes, 1.0 equiv) were successively added at -95 °C. The yellow solution was stirred 5 min at -95 °C and an 1.0 M etheral solution of ZnBr2 (1.0 equiv) was added dropwise. The resulting white suspension of allenylzinc bromide (±)-1 was then allowed to warm up to r.t. and a 0.3 M etheral solution of sulfinimine (±)-2 (0.66 to 0.16 equiv) was immediately added. After 18 h stirring at r.t., the solution was quenched with a 30% aq NH3 /sat. aq NH4 Cl, a 1:2 solution. The layers were separated and the aqueous one was extracted with Et2 O (3×). The combined organic layers were washed with H2 O and brine, dried over anhyd Na2 SO4 and concentrated in vacuo. The residual brownish oil was purified by flash chromatography over silica gel to give the corresponding diastereomerically pure trans -ethynyl N -sulfinylaziridine (±)-3 .
14a Jones GB.
Wright JM.
Plourde GW.
Hynd G.
Huber RS.
Mathews JE.
J. Am. Chem. Soc.
2000,
122:
1937
14b Wright JM.
Jones GB.
Tetrahedron Lett.
1999,
40:
7605
14c Hynd G.
Jones GB.
Plourde GW.
Wright JM.
Tetrahedron Lett.
1999,
40:
4481
14d McPhee MM.
Kerwin SM.
J. Org. Chem.
1996,
61:
9385
14e Jones GB.
Huber RS.
Mathews JE.
J. Chem. Soc., Chem. Commun.
1995,
1791
14f Huber RS.
Jones GB.
Tetrahedron Lett.
1994,
35:
2655
15 CCDC 230643 contains the supplementary crystallographic data for compound (±)-3g . These data can be obtained free of charge via www.ccdc.ac.uk/conts/retrieving.html [or from Cambridge Cystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax:+44(1223)336033; or deposit@ccdc.cam.ac.uk].
16 In the case of N -sulfonylimines, for which low selectivities are obtained (see ref. 10a), such a coordination of the zinc by the sulfonyl group has not been envisaged because of weak Lewis basicity of both nitrogen and oxygen atoms.
17a Davis FA.
Ramachandar T.
Wu Y.
J. Org. Chem.
2003,
68:
6894
17b Tang TP.
Volkman ST.
Ellman JA.
J. Org. Chem.
2001,
66:
8772
17c Davis FA.
Liu H.
Zhou P.
Fang T.
Reddy GV.
Zhang Y.
J. Org. Chem.
1999,
64:
7559
17d Tang TP.
Ellman JA.
J. Org. Chem.
1999,
64:
12
18 Davis FA.
Prasad KR.
J. Org. Chem.
2003,
68:
7249
19a Cainelli G.
Galletti P.
Giacomini D.
Orioli P.
Angew. Chem. Int. Ed.
2000,
523
19b Cainelli G.
Giacomini D.
Galletti P.
Chem. Commun.
1999,
567
20 Kolodiazhnyi OI.
Tetrahedron
2003,
59:
5953
21a Poisson J.-F.
Chemla F.
Normant JF.
Synlett
2001,
305
21b Poisson J.-F.
Normant JF.
J. Am. Chem. Soc.
2001,
123:
4639
