Chlorobenzene → Biphenyl

HRID 636903Notes

Reaction equation

HRID 636903 reaction equation
[C:1]1(B(O)O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cl:10][C:11]1[CH:12]=[N:13][CH:14]=[CH:15][CH:16]=1.Cl[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>[Pd].[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:1]1([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cl:10][C:11]1[CH:12]=[N:13][CH:14]=[CH:15][CH:16]=1

Participants

7

Reactant 3

HCID 7964Chlorobenzene2×HCID 122873-ChloropyridineHCID 66827Phenylboronic Acid

Product 2

HCID 7095BiphenylYield 28%HCID 122873-Chloropyridine

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalyst

Procedure

Ali et al., Tetrahedron, vol 48 (1992), pp. 8117-8126 discloses Suzuki-type cross-coupling reactions of arylboronic acids with pi-electron deficient heteroaryl chlorides (chloropyridines, chloropyrimidines, and chloropyrazines, chloroquinolines). These authors state, “It is widely accepted that palladium-catalyzed cross coupling reactions of arylboronic acids, and indeed of other organometallic species, proceed best with aryl or heteroaryl bromides or iodides, and either poorly, or more commonly, not at all with the corresponding chlorides.” These investigators confirmed early literature reports that reaction of phenylboronic acid with either chlorobenzene or 3-chloropyridine in the presence of tetrakis(triphenylphosphine) palladium failed to produce any coupled product. Using Pd(bis-1,4-(diphenylphosphino)butane)Cl2, however, they were able to get chlorobenzene to react to give 28% of biphenyl, and 3-chloropyridine was converted to 3-phenylpyridine in 71% yield. Among 2-chloropyridines, the reaction tolerated some (3-nitro, 5-chloro) but not other (3-OH, 3-CONH2) substituents.

Workup

  1. customto produce any coupled product
  2. customto react

Sources & evidence

ORD record
ord-794f0b61d14847438f816e73b4f65218
Source dataset
uspto-grants-2001_02
Patent number
US06194599B1

Reaction notes

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