Abstract
A one-step conversion of alcohols into thioesters under solvent-free
conditions is reported. The alcohols were reacted with primary thioamides
in the presence of p -toluenesulfonic
acid under solvent-free conditions to produce the corresponding
thioesters in good to excellent yields.
Key words
alcohols - carbocations - esters - sulfur - green chemistry
References and Notes
<A NAME="RG24710ST-1">1 </A>
Vallari DS.
Jackowski S.
Rock CO.
J.
Biol. Chem.
1987,
262:
2468
<A NAME="RG24710ST-2">2 </A>
Stindl A.
Keller U.
J. Biol. Chem.
1993,
268:
10612
<A NAME="RG24710ST-3">3 </A>
Dittmann J.
Wenger RM.
Kleinkauf H.
Lawen A.
<A NAME="RG24710ST-4">4 </A>
Stachelhaus T.
Huser A.
Marahiel MA.
Chem.
Biol.
1996,
3:
913
<A NAME="RG24710ST-5">5 </A>
Kanda Y.
Ashizawa T.
Kakita S.
Takahashi Y.
Kono M.
Yoshida M.
Saitoh Y.
Okabe M.
J. Med. Chem.
1999,
42:
1330
<A NAME="RG24710ST-6">6 </A>
Mroszczak E, and
Runkel R. inventors; US Patent 4 397 862.
; Chem. Abstr.
1983 , 99 , 146134
<A NAME="RG24710ST-7">7 </A>
Venuti MC.
Young GM.
Maloney PG.
Johnson D.
McGreevy K.
Pharm. Res.
1989,
6:
867
<A NAME="RG24710ST-8">8 </A>
Greenlee ML.
Laub JB.
Balkovec JM.
Hammond ML.
Hammond GG.
Pompliano DL.
Epstein-Toney JH.
Bioorg. Med.
Chem. Lett.
1999,
9:
2549
<A NAME="RG24710ST-9">9 </A>
Olsen J.
Bjørnsdottir I.
Tjørnelund J.
Hansen SH.
<A NAME="RG24710ST-10">10 </A>
Matsumoto K.
Costner EA.
Nishimura I.
Ueda M.
Willson CG.
Macromolecules
2008,
41:
5674
<A NAME="RG24710ST-11">11 </A>
Kricheldorf HR.
Schwarz G.
J. Macromol. Sci., Part A: Pure
Appl. Chem.
2007,
44:
625
<A NAME="RG24710ST-12">12 </A>
Kameyama A.
Kimura Y.
Nishikubo T.
Macromolecules
1997,
30:
6494
<A NAME="RG24710ST-13">13 </A>
Yang W.
Drueckhammer DG.
J. Am. Chem.
Soc.
2001,
123:
11004
14a </A>
Johnson JS.
Evans DA.
Acc. Chem. Res.
2000,
33:
325
14b </A>
Fortner KC.
Shair MD.
J.
Am. Chem. Soc.
2007,
129:
1032
14c </A>
Gennari C.
Vulpetti A.
Pain G.
Tetrahedron
1997,
53:
5909
14d </A>
Kobayashi S.
Uchiro H.
Fujishita Y.
Shiina I.
Mukaiyama T.
J.
Am. Chem. Soc.
1991,
113:
4247
<A NAME="RG24710ST-15">15 </A>
Boeini ZH.
Kashan EM.
Green Chem.
2009,
11:
1987
<A NAME="RG24710ST-16">16 </A>
Gopinath P.
Vidyarini RS.
Chandrasekaran S.
J. Org. Chem.
2009,
74:
6291
<A NAME="RG24710ST-17">17 </A>
Basu B.
Paul S.
Nanda AK.
Green
Chem.
2010,
5:
767
<A NAME="RG24710ST-18">18 </A>
Krayushkin MM.
Lichitskii BV.
Mikhalev AP.
Nabatov BV.
Dudinov AA.
Ivanov SN.
Russ.
J. Org. Chem.
2006,
42:
860
19a </A>
Jagodzinski ST.
Chem. Rev.
2003,
103:
197
19b </A>
Moghaddam MF.
Boeini ZH.
Synlett
2005,
1612
20a </A>
Ralston AW.
Vander Wal RJ.
McCorkel MR.
20b </A>
Zbruyev OI.
Stiasni N.
Kappe CO.
J. Comb. Chem.
2003,
5:
145
20c </A>
Charette
AB.
Grenon M.
J. Org. Chem.
2003,
68:
5792
20d </A>
Olsson R.
Hansen HC.
Andersson CM.
Tetrahedron Lett.
2000,
41:
7947
20e </A>
Polshettiwar V.
Kaushik MP.
Tetrahedron Lett.
2006,
47:
2315
21 </A>
Complete experimental procedures and
relevant ¹ H and
¹³ C
NMR spectra and elemental microanalyses for new compounds are available
in the Supporting Information
<A NAME="RG24710ST-22">22 </A>
General Procedure :
In a round-bottom flask, thioamide (1 mmol), alcohol (1.2 mmol),
and p -TsOH (1 mmol) were heated to melt
and heating was continued at 100 ˚C for 60 min.
The reaction mixture was then poured into H2 O (10 mL)
with vigorous stirring. Thereafter an oily residue was left, which
soon solidified to a semi-crystalline mass. The solid was filtered
and washed with H2 O (2 × 10 mL).
Finally the solid compound was recrystallized from EtOH (95%)
to afford pure thioesters as white or pale-yellow needles with a characteristic
odor. Compound 3s : Mp 127-129 ˚C
(EtOH); ¹ H NMR (400 MHz, CDCl3 ): δ = 7.86
(d, J = 7.6 Hz,
2 H), 7.40 (d, J = 7.6 Hz,
2 H), 2.27 (m, 6 H), 2.11 (s, 3 H), 1.75-1.85
(m, 6 H); ¹³ C NMR (100 MHz,
CDCl3 ): δ = 191.3, 139.2, 136.7, 128.7,
128.3, 51.5, 41.9, 36.3, 29.9; Anal. Calcd for C17 H19 ClOS:
C, 66.54; H, 6.24; S, 10.45. Found: C, 66.75; H, 6.09; S, 10.59
