Abstract
A range of functionalized aryl and heteroaryl disulfides has been prepared from zinc
organometallics by using sulfur monochloride (S2Cl2). The zinc reagents were obtained by transmetalation from magnesium or lithium reagents
with ZnBr2.
Key words
zinc organometallic reagents - sulfur monochloride - aryl disulfides - heteroaryl
disulfides - functionalized arylmagnesium halides
References
<A NAME="RG06105ST-1">1</A>
Uemura S. In
Comprehensive Organic Synthesis
Vol. 7:
Trost BM.
Fleming I.
Ley SV.
Pergamon Press;
Oxford:
1991.
p.757-787
<A NAME="RG06105ST-2">2</A>
Solladié G. In
Comprehensive Organic Synthesis
Vol. 6:
Trost BM.
Fleming I.
Winterfeldt E.
Pergamon Press;
Oxford:
1991.
p.133-170
<A NAME="RG06105ST-3A">3a</A>
Tan RX.
Jensen PR.
Williams PG.
Fenical W.
J. Nat. Prod.
2004,
67:
1374
<A NAME="RG06105ST-3B">3b</A>
Eisenbarth S.
Gehling M.
Harder A.
Steffan B.
Tetrahedron
2002,
58:
8461
<A NAME="RG06105ST-3C">3c</A>
Nicholas GM.
Blunt JW.
Munro MHG.
J. Nat. Prod.
2001,
64:
341
<A NAME="RG06105ST-3D">3d</A>
Nicolaou KC.
Hughes R.
Pfefferkorn JA.
Barluenga S.
Roecker AJ.
Chem.-Eur. J.
2001,
7:
4280
<A NAME="RG06105ST-3E">3e</A>
Kim D.
Lee IS.
Jung JH.
Yang S.-I.
Arch. Pharm. Res.
1999,
22:
25
<A NAME="RG06105ST-3F">3f</A>
Tamamura H.
Matsumoto F.
Sakano K.
Otaka A.
Fujii N.
Chem. Commun.
1998,
151
<A NAME="RG06105ST-3G">3g</A>
Kang H.
Fenical W.
Tetrahedron Lett.
1996,
37:
2369
<A NAME="RG06105ST-3H">3h</A>
Akaji K.
Fujino K.
Tatsumi T.
Kiso Y.
J. Am. Chem. Soc.
1993,
115:
11384
<A NAME="RG06105ST-4">4</A>
Knochel P.
Millot N.
Rodriguez AL.
Tucker CE.
Org. React. (N. Y.)
2001,
58:
417
<A NAME="RG06105ST-5A">5a</A>
Langhals H.
Wahner B.
Polborn K.
Tetrahedron
1996,
52:
1961
<A NAME="RG06105ST-5B">5b</A>
Derbesy G.
Harpp DN.
Tetrahedron Lett.
1994,
35:
5381
<A NAME="RG06105ST-5C">5c</A>
Okazaki R.
Inoue K.
Inamoto N.
Tetrahedron Lett.
1979,
3673
<A NAME="RG06105ST-5D">5d</A>
Zysman-Colman E.
Harpp DN.
J. Org. Chem.
2003,
68:
2487
<A NAME="RG06105ST-5E">5e</A>
Huang NZ.
Lakshmikantham MV.
Cava MP.
J. Org. Chem.
1987,
52:
169
<A NAME="RG06105ST-5F">5f</A>
Yang X.
Rauchfuss TB.
Wilson SR.
J. Am. Chem. Soc.
1989,
111:
3465
<A NAME="RG06105ST-6">6</A>
Knochel P.
Dohle W.
Gommermann N.
Kneisel FF.
Kopp F.
Korn T.
Sapountzis I.
Vu VA.
Angew. Chem. Int. Ed.
2003,
42:
4302 ; Angew. Chem. 2003, 115, 4438
<A NAME="RG06105ST-7">7</A>
Burns TP.
Rieke RD.
J. Org. Chem.
1987,
52:
3674
<A NAME="RG06105ST-8">8</A>
Krasovskiy A.
Knochel P.
Angew. Chem. Int. Ed.
2004,
43:
3333 ; Angew. Chem. 2004, 116, 3396
<A NAME="RG06105ST-9A">9a</A>
Guillaneux D.
Kagan HB.
J. Org. Chem.
1995,
60:
2502
<A NAME="RG06105ST-9B">9b</A>
Liu C.-M.
Lou S.-J.
Liang Y.-M.
Synth. Commun.
1998,
28:
2271
<A NAME="RG06105ST-10A">10a</A>
Sakamoto T.
Nagano T.
Kondo Y.
Yamanaka H.
Chem. Pharm. Bull.
1988,
36:
2248
<A NAME="RG06105ST-10B">10b</A>
Achab S.
Guyot M.
Potier P.
Tetrahedron Lett.
1995,
36:
2615
<A NAME="RG06105ST-10C">10c</A>
Fürstner A.
Ernst A.
Krause H.
Ptock A.
Tetrahedron
1996,
52:
7329
<A NAME="RG06105ST-11A">11a</A>
Achad S.
Guyot M.
Potier P.
Tetrahedron Lett.
1995,
36:
2615
<A NAME="RG06105ST-11B">11b</A>
Sapountzis I.
Knochel P.
Angew. Chem. Int. Ed.
2004,
43:
897 ; Angew. Chem. 2004, 116, 915
<A NAME="RG06105ST-12">12</A>
Typical Procedure. Preparation of the Functionalized Indolyl Disulfide 2k.
A dry and nitrogen flushed 25 mL Schlenk flask, equipped with a rubber septum and
a magnetic stirring bar, was charged with dry THF (5.0 mL) and 3-iodo-1-(phenyl-methyl)-1H-indole-2-carboxylic acid ethyl ester (403 mg, 0.99 mmol). The solution was cooled
to -20 °C and
i-PrMgCl (1.12 mL, 1.00 mmol, 0.9 M in THF) was added slowly. The reaction mixture
was stirred at that temperature until the I/Mg-exchange was complete (0.5 h, checked
by GC), cooled to -40 °C, ZnBr2 (0.64 mL, 1.09 mmol, 1.7 M in THF) was added and the white suspension was stirred
for 30 min at that temperature. The heterogeneous mixture was cooled to -80 °C and
S2Cl2 (67 mg, 0.50 mmol) was added dropwise. After 10 min the reaction mixture was quenched
with sat. NH4Cl solution (50 mL), extracted with Et2O (3 × 50 mL), the combined organic layers were washed with brine (50 mL), dried over
MgSO4 and concentrated in vacuo. Flash chromatographic purification on silica gel (pentane-Et2O = 3:1) furnished 2k as a light yellow solid (193 mg, 0.31 mmol, 62%, mp >240 °C decomposition).