Abstract
A novel synthetic application of the hypervalent iodine reagent,
(diacetoxyiodo)benzene, and catalytic amount of sodium azide in
acetonitrile for oxidative decarboxylation of 2-aryl carboxylic
acids into corresponding aldehydes, ketones, and nitriles at room
temperature is described. The advantages of this protocol are shorter
reaction times and mild reaction conditions to obtain moderate to
good yields
Key words
(diacetoxyiodo)benzene - decarboxylation - aldehydes - ketones - nitriles
References and Notes
1a </A>
Telvekar VN.
Takale B.
Tetrahedron
Lett.
2010,
49:
2213
1b </A>
Telvekar VN.
Rane RM.
Tetrahedron
Lett.
2007,
48:
6051
2a </A>
Kotali A.
Harris PA.
J.
Heterocycl. Chem.
1996,
33:
605
2b </A>
Kotali A.
Tetrahedron
Lett.
1994,
36:
6753
2c </A>
Karade NN.
Shirodkar SG.
Patil MN.
Potrekar
RA.
Karade HN.
Tetrahedron Lett.
2003,
44:
6729
2d </A>
Yusubov MS.
Chi K.-W.
Park JY.
Karimov R.
Zhdankin VV.
Tetrahedron Lett.
2006,
47:
6305
<A NAME="RD19210ST-3">3 </A>
Westheimer FH.
Chem.
Rev.
1949,
45:
419
<A NAME="RD19210ST-4">4 </A>
Rigby W.
J.
Chem. Soc.
1950,
1907
<A NAME="RD19210ST-5">5 </A>
Sheldon RA.
Kochi JK.
Org. React.
1972,
19:
279
<A NAME="RD19210ST-6">6 </A>
Nakagawa K.
Igano K.
Sugita J.
Chem.
Pharm. Bull.
1964,
12:
403
<A NAME="RD19210ST-7">7 </A>
Santaniello E.
Manzocchi A.
Farachi C.
Synthesis
1980,
563
<A NAME="RD19210ST-8">8 </A>
Beebe TR.
Adkins RL.
Belcher AI.
Chay T.
Fuller AE.
Morgan VL.
Sencherey BB.
Russell LJ.
Yates SW.
J. Org. Chem.
1982,
47:
3006
<A NAME="RD19210ST-9">9 </A>
Santaniello E.
Ponti F.
Manzocchi A.
Tetrahedron
Lett.
1980,
21:
2655
10a </A>
Tangestaninejad S.
Mirkhani V.
J.
Chem. Res., Synop.
1998,
820
10b </A>
Moghadam M.
Tangestaninejad S.
Mirkhani V.
Mohammadpoor-baltork I.
Sirjanian N.
Parand S.
Bioorg. Med. Chem.
2009,
17:
3394
10c </A>
Nasr-Esfahani M.
Montazerozohori M.
Akhlaghi P.
Bull. Korean Chem. Soc.
2009,
30:
1583
<A NAME="RD19210ST-11">11 </A>
Stevenson GW.
Luck JM.
J. Biol. Chem.
1961,
236:
715
<A NAME="RD19210ST-12">12 </A>
Friedman AH.
Morgulis S.
J. Am. Chem. Soc.
1936,
58:
909
<A NAME="RD19210ST-13">13 </A>
Dakin HD.
Biochem.
J.
1917,
11:
79
<A NAME="RD19210ST-14">14 </A>
Takeda T.
Yamauchi S.
Fujiwara T.
Synthesis
1996,
600
<A NAME="RD19210ST-15">15 </A>
Hiegal G.
Lewis J.
Bae J.
Synth.
Commun.
2004,
34:
3449
<A NAME="RD19210ST-16">16 </A>
Moriarty MR.
Sultana M.
Ku Y.-Y.
J.
Chem. Soc., Chem. Commun.
1985,
974
<A NAME="RD19210ST-17">17 </A>
Representative
Procedure for Decarboxylation of Phenylacetic Acid (Table 1, Entry
1)
3 (0.12
equiv) in MeCN (10 mL) were stirred at 0 ˚C for 2 min,
then phenyl acetic acid (1 equiv) was added to the stirred solution.
The reaction mixture was allowed to come at r.t. and stirring continued
until completion of reaction (TLC), when it was quenched with H2 O
(25 mL) and extracted with CHCl3 (3 × 10
mL). The combined organic layers were washed with dilute NaHCO3 (20
mL), followed by H2 O (3 × 20
mL), dried over Na2 SO4 , and concentrated in
vacuo. The residue was purified by column chromatography on silica
gel (hexane-EtOAc = 9:1) to
yield benzaldehyde (88%) as a colorless liquid.
<A NAME="RD19210ST-18">18 </A>
Representative
Procedure for Decarboxylation of α-Amino(phenyl)acetic
Acid (Table 1, Entry 13)
3 (0.12 equiv) in MeCN (10 mL) were stirred
at r.t. for 2 min, then α-amino-(phenyl)acetic acid (1
equiv) was added to the stirred solution. Stirring was continued
until completion of reaction (TLC), when it was quenched with H2 O
(25 mL) and worked up as mentioned above to yield benzonitrile (90%)
as a colorless liquid; bp 188 ˚C. IR (neat): 2230,
2256, 2178, 1682, 1572, 1492 cm-¹ . ¹³ C
NMR (75 MHz, CDCl3 ): δ = 132.84, 132.10,
129.21, 118.82, 112.41.
