Table 1 Optimization of the reaction conditionsa

From: Regioselective and site-divergent synthesis of tetrahydropyridines by controlled reductive-oxidative dearomative hydroarylation of pyridinium salts

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Entry

Catalyst

Oxidant

Additive (x equiv)

Yield of 3a (%)

Yield of 4a (%)

1

[Co-1]

TBPB

/

8

10

2

[Co-1]

TBPB

K3PO4 (0.5)

50

18

3

[Co-1]

TBPB

K2CO3 (0.5)

32

20

4

[Co-1]

TBPB

t-BuOK (0.5)

36

14

5

[Co-1]

DTPB

K3PO4 (0.5)

26

15

6

[Co-1]

BPO

K3PO4 (0.5)

26

Trace

7

[Co-1]

m-CPBA

K3PO4 (0.5)

Trace

Trace

8

[Co-1]

TBPB

Mn(OAc)2 (1.0)

70

30

9

[Co-2]

TBPB

Mn(OAc)2 (1.0)

60

8

10

[Co-2]

TBPB

Mn(OAc)2‧4H2O (1.0)

70

10

11b

[Co-2]

TBPB

Mn(OAc)2‧4H2O (0.6)

95% (89%)c

Trace

12

/

/

AgTFA (2.0)

N.D.

48

13

/

/

AgOAc (2.0)

N.D.

N.D.

14

/

/

AgF (2.0)

N.D.

34

15

/

/

KF (2.0)

N.D.

N.D.

16

/

/

CsF (2.0)

N.D.

N.D.

17

/

/

Ae

N.D.

99% (94%)c

18 d

/

/

Ae

N.D.

84

19 d

/

/

Bf

N.D.

60

20 d

/

/

Cg

N.D.

38

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  1. aEntries 1–7: Reaction was conducted using 1a (0.10 mmol) and 2a (0.12 mmol) under indicated conditions. Entries 8–10: Reaction was conducted using 1a (0.20 mmol) and 2a (0.10 mmol) under indicated conditions. Entries 12–17: Reaction was conducted using 1a (0.20 mmol) and 2a (0.10 mmol) under indicated conditions.
  2. b1a (0.25 mmol) and 2a (0.10 mmol), [Co-2] (6.0 mol%), TBPB (3.0 equiv), Mn(OAc)2•4H2O (0.6 equiv) were used.
  3. cIsolated yield.
  4. d1a (0.15 mmol) and 2a (0.10 mmol) were used.
  5. eA: Methyl 2,2-difluoro-2-(fluorosulfonyl)acetate.
  6. fB: Trimethylsilyl 2-(fluorosulfonyl)difluoroacetate.
  7. gC: 2-(Fluorosulfonyl)difluoroacetic acid.