Abstract
N -Formylsaccharin, a very cheap reagent,
has been revealed to be an efficient and chemoselective formylating
agent of amines.
Key words
formylation - amine - amino alcohol - saccharin
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28 Chiyomaru I, Yoshinaga E, and Ito H. inventors; JP 48008500. The preparation of 1 was performed according to:
Typical Procedure
Formic acid
(20 mmol, 2 equiv) and Ac2 O (20 mmol, 2 equiv) were stirred
at 60 ˚C for 2 h and saccharin (1.83 g, 10 mmol,
1 equiv) was added in one portion. The reaction mixture was stirred
for 5 h at 60 ˚C. Water was added (10 mL), and
the white precipitate was filtered to afford pure
N- formylsaccharin
(1.9 g, 9 mmol, 90%)
29
Typical Procedure
for Amines
To a suspension of N -formylsaccharin
(211 mg, 1 mmol, 1 equiv) in anhyd THF (1 mL) at r.t., the requisite
primary or secondary amine was added (1 mmol, 1 equiv). After 15
min at r.t., the reaction mixture was diluted with CH2 Cl2 (10
mL), and a sat. aq NaHCO3 solution (10 mL) was added,
the layers were separated, and the aqueous layer extracted with
CH2 Cl2 (2 × 10
mL). The combined organic layers were dried over MgSO4 ,
filtered, and concentrated in vacuo to afford pure
30
Typical Procedure
for Amino Alcohols
To a suspension of N -formylsaccharin (211 mg, 1 mmol, 2 Cl2 (5 mL), (piperidinomethyl)polystyrene
(loading: 4 mmol/g, 750 mg) was added, and the reaction
mixture was stirred at r.t. After 10 min, the reaction mixture was
filtered through Celite® and concentrated in
vacuo to afford pure N-formylated amino alcohols.
