Abstract
A regioselective method for highly efficient C-N and C-S bond formation with 2-halobenzoic acids is described. The Cu/Cu2 O-catalyzed reaction is carried out in 2-ethoxyethanol or ethylene glycol diethyl ether and does not require the use of strong base or other additives. This procedure eliminates the need for acid protection, tolerates a wide range of functional groups and provides aromatic and aliphatic amines and sulfides in 81-99% yield.
Key words
amines - thiols - halobenzoic acids - carbon-heteroatom bond formation
References
1a Ottolia M.
Toro L.
Biophys. J.
1994,
67:
2272
1b Farrugia G.
Nitecki S.
Harty GJ.
Camilleri M.
Szurszewski JH.
Gut
1998,
42:
258
2a Green NS.
Palaninathan SK.
Sacchettini JC.
Kelly JW.
J. Am. Chem. Soc.
2003,
125:
13404
2b Klabunde T.
Petrassi HM.
Oza VB.
Raman P.
Kelly JW.
Saccettini JC.
Nat. Struct. Biol.
2000,
7:
312
2c Oza VB.
Smith C.
Raman B.
Koepf EK.
Lashuel HA.
Petrassi HM.
Chiang KP.
Powers ET.
Sachettinni J.
Kelly JW.
J. Med. Chem.
2002,
45:
321
3a Inai Y.
Kurokawa Y.
Ida A.
Hirabayashi T.
Bull. Chem. Soc. Jpn.
1999,
72:
55
3b Ramesh K.
Balaram P.
Bioorg. Med. Chem.
1999,
7:
105
3c Abele S.
Seebach D.
Eur. J Org. Chem.
2000,
1
3d Inai Y.
Tagawa K.
Takasu A.
Hirabayashi T.
Oshikawa T.
Yamashita M.
J. Am. Chem. Soc.
2000,
122:
11731
3e Inai Y.
Ousaka N.
Okabe T.
J. Am. Chem. Soc.
2003,
125:
8151
4 Ullmann F.
Ber. Dtsch. Chem. Ges.
1903,
36:
2382
5a Kwong FY.
Klapars A.
Buchwald SL.
Org. Lett.
2002,
4:
581
5b Wolf C.
Mei X.
J. Am. Chem. Soc.
2003,
125:
10651
5c Docampo Palacios ML.
Pello Comdom RF.
Synth. Commun.
2003,
33:
1771
5d Kunz K.
Scholz U.
Ganzer D.
Synlett
2003,
2428
5e Huang X.
Anderson KW.
Zim D.
Jiang L.
Klapars A.
Buchwald SL.
J. Am. Chem. Soc.
2003,
125:
6653
5f Dokorou V.
Kovala-Demertzi D.
Jasinski JP.
Galani A.
Demertzis MA.
Helv. Chim. Acta
2004,
87:
1940
5g Mei X.
Wolf C.
Chem. Commun.
2004,
2078
5h Mei X.
Wolf C.
J. Am. Chem. Soc.
2004,
126:
14736
5i Mei X.
Wolf C.
J. Org. Chem.
2005,
70:
2299
6 Stauffer SR.
Steinbeiser MA.
Tetrahedron Lett.
2005,
46:
2571
7 Csuk R.
Barthel A.
Raschke C.
Tetrahedron
2004,
60:
5737
8a Beard RL.
Colon DF.
Song TK.
Davies PJA.
Kochhar DM.
Chandraratna RAS.
J. Med. Chem.
1996,
39:
3556
8b Potin D.
Parnet V.
Teulon J.-M.
Camborde F.
Caussade F.
Meignen J.
Provost D.
Cloarec A.
Bioorg. Med. Chem. Lett.
2000,
10:
805
9a Kwong FY.
Buchwald SL.
Org. Lett.
2002,
4:
3517
9b Fernandez-Rodriguez MA.
Shen Q.
Hartwig JF.
J. Am. Chem. Soc.
2006,
128:
2180
10 Kalinin AV.
Bower JF.
Riebel P.
Snieckus V.
J. Org. Chem.
1999,
64:
2986
11 Geertsma EM.
Hoen R.
Meetsma A.
Feringa BL.
Eur. J. Org. Chem.
2006,
3596
12a Mei X.
August AT.
Wolf C.
J. Org. Chem.
2006,
71:
142
12b Wolf C.
Liu S.
Mei X.
August AT.
Casimir MD.
J. Org. Chem.
2006,
71:
3270
13a Maradolla MB.
Amaravathi M.
Kumar VN.
Mouli GVPC.
J. Mol. Catal. A: Chem.
2007,
266:
47
13b Rodriguez-Dominguez JC.
Balbuzano-Deus A.
Lopez-Lopez MA.
Kirsch G.
J. Heterocycl. Chem.
2007,
44:
273
14 No product formation was observed in the absence of a copper catalyst.
15 Carbon-sulfide bond formation with 2-iodobenzoic acids proved to be complete within two hours, while 2-chloro-benzoic acids gave low yields under the conditions described.
16a Luyt LG.
Katzenellenbogen JA.
Bioconjugate Chem.
2002,
13:
1140
16b Zarghi A.
Faizi M.
Shafaghi B.
Ahadian A.
Khojastehpoor HR.
Zanganeh V.
Tabatabai SA.
Shafiee A.
Bioorg. Med. Chem. Lett.
2005,
15:
3126
16c Khan S.
Bernad PL.
Korshun VA.
Southern EM.
Shchepinov MS.
Synlett
2005,
2453
16d Ko J.
Ham J.
Yang I.
Chin J.
Nam S.
Kang H.
Tetrahedron Lett.
2006,
47:
7101
17 Pellon RF.
Estevez-Braun A.
Docampo ML.
Martin A.
Ravelo AG.
Synlett
2005,
1606
18 Kirk K.
Horner HA.
Biochem. J.
1995,
311:
761
19 Kohno Y.
Awano K.
Miyashita M.
Fujimori S.
Kuriyama K.
Sakoe Y.
Kudoh S.
Saito K.
Kojima E.
Bioorg. Med. Chem. Lett.
1997,
7:
1515
20 Hiroi K.
Suzuki Y.
Abe I.
Tetrahedron: Asymmetry
1999,
10:
1173
21 Liao Y.
Venhuis BJ.
Rodenhuis N.
Timmerman W.
Wikstroem H.
Meier E.
Bartoszyk GD.
Boettcher H.
Seyfried CA.
Sundell S.
J. Med. Chem.
1999,
42:
2235
22 Parlow JJ.
Stevens AM.
Stegeman RA.
Stallings WC.
Kurumbail RG.
South MS.
J. Med. Chem.
2003,
46:
4297
23 Arya VP.
Sudarsanam V.
Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.
1977,
15:
145
