Table 1 Reaction Conditions Optimization for Polyol Esters and Nucleophilesa

From: Catalytic amidation of natural and synthetic polyol esters with sulfonamides

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Polyol ester, 1

Nucleophile, 2

Catalyst

mol %

Temp /°C

Yield /%

1

Glycol diacetate (1a)

TsNHMe (2a)

Hf(OTf)4

2

120

90

2

Glycol dipropionoate (1b)

TsNHMe (2a)

Hf(OTf)4

2

120

83

3

Glycol diisobutyrate (1c)

TsNHMe (2a)

Hf(OTf)4

2

120

84

4

Glycol dipivalate (1d)

TsNHMe (2a)

Hf(OTf)4

2

120

83

5

Triacetin (1e)

TsNHMe (2a)

Hf(OTf)4

5

120

42

6

Tributyrin (1f)

TsNHMe (2a)

Hf(OTf)4

5

120

48

7b

Glycol diacetate (1a)

TsNH2 (2b)

Hf(OTf)4

2

120

85

8

Glycol diacetate (1a)

AcNHMe (2c)

Hf(OTf)4

2

120

0

9

Glycol diacetate (1a)

BocNHMe (2d)

Hf(OTf)4

2

120

0

10

Glycol diacetate (1a)

Phthalimide (2e)

Hf(OTf)4

2

120

0

11

Glycol diacetate (1a)

CH3SO2NHMe (2f)

Hf(OTf)4

2

120

92

12

Glycol diacetate (1a)

PhSO2NHMe (2g)

Hf(OTf)4

2

120

94

13

Glycol diacetate (1a)

4-BrPhSO2NHMe (2h)

Hf(OTf)4

2

120

95

14

Glycol diacetate (1a)

4-CF3PhSO2NHMe (2i)

Hf(OTf)4

2

120

98

15

Glycol diacetate (1a)

4-MeOPhSO2NHMe (2j)

Hf(OTf)4

2

120

91

16

Glycol diacetate (1a)

4-NO2PhSO2NHMe (2k)

Hf(OTf)4

2

120

0

17

Glycol diacetate (1a)

4-AcNHPhSO2NHMe (2l)

Hf(OTf)4

2

120

0

18

Glycol diacetate (1a)

Saccharin (2m)

Hf(OTf)4

2

120

98

19c

Tributyrin (1f)

Saccharin (2m)

Hf(OTf)4

2

120

60

20c

Tributyrin (1f)

Saccharin (2m)

Hf(OTf)4

5

120

66

21c

Tributyrin (1f)

Saccharin (2m)

Yb(OTf)3

5

120

40

22c

Tributyrin (1f)

Saccharin (2m)

Al(OTf)3

5

120

45

23c

Tributyrin (1f)

Saccharin (2m)

Sc(OTf)3

5

120

76

24c

Tributyrin (1f)

Saccharin (2m)

Sc(OTf)3

5

150

85

25c,d

Tributyrin (1f)

Saccharin (2m)

Sc(OTf)3

2

150

90

26c,e

Tributyrin (1f)

Saccharin (2m)

Sc(OTf)3

2

150

66

27c,f

Tributyrin (1f)

Saccharin (2m)

Sc(OTf)3

2

150

65

  1. Tf  trifluoromethanesulfonyl, Ts 4-methylbenzenesulfonyl, Ac acetyl, Boc t-butyloxycarbonyl, neat without solvent
  2. a1 (1.0 mmol), 2 (0.5 mmol) and catalyst were stirred at 120 °C for 24 h; Yields are isolated unless otherwise noted
  3. bReaction time: 14 h. N,N-dialkylated product 10% obtained
  4. cNMR yield
  5. d85% isolated yield, along with 3% double substitution
  6. e1:1 of tributyrin and saccharin, product contains 14% double substitution product
  7. f1:2 of tributyrin and saccharin, product contains 25% double substitution product
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