Table 1 Optimization of the reaction conditionsa.

From: Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species

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Entry

Cat.

Ligand

Yield (%)

1b

Pd(OAc)2

dppp

n.d.

2

Cu(OAc)2

dppp

n.d.

3

Co(acac)2

dppp

n.d.

4

Ni(COD)2

dppp

2

5

NiBr2

dppp

17

6

Ni(acac)2

dppp

20

7c

Ni(acac)2

dppp

37

8c

Ni(acac)2

dppe

4

9c

Ni(acac)2

dppb

5

10c

Ni(acac)2

dppf

10

11c

Ni(acac)2

PPh3

n.d.

12c

Ni(acac)2

Tripod

64

13c

Ni(acac)2

Triphos

81

14c,d

Ni(acac)2

Triphos

16

15c,e

Ni(acac)2

Triphos

5

  1. NMP 1-methyl-2-pyrrolidinone, DMI 1,3-dimethyl-2-imidazolidinone, acac acetylacetonate, COD 1,5-cyclooctadiene, dppp 1,3-bis(diphenylphosphino)propane, dppe 1,2-bis(diphenylphosphino)ethane, dppb 1,4-bis(diphenylphosphino)butane, dppf 1,1’-bis(diphenylphosphino)ferrocene, Tripod 1,1,1-Tris(diphenylphosphinomethyl)ethane, Triphos bis(2-diphenylphosphinoethyl)phenylphosphine, PMHS poly(methylhydrosiloxane), n.d. not detected.
  2. aReaction conditions: 1a (0.125 mmol), CO2/NH3 (1/1 atm), NMP (0.5 mL), 20 h; GC yield.
  3. b5 mol% Pd(OAc)2.
  4. cWith 1.0 equiv. of Zn powder.
  5. dDMI as solvent.
  6. ePMHS was used instead of PhSiH3.
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