Application Guide for Palladium

Catalyzed Cross-Coupling Reactions

Common Cross-Coupling Reactions

Negishi (C-C)
R1X

Heck (C-C)
[Pd]

R2ZnX

R1 R2

R1 = alkenyl, (hetero)aryl, alkynyl, acyl

R2 = alkenyl, (hetero)aryl, alkynyl, alkyl
X = Cl, Br, I, OTf, OAc

R2B(Y)2

[Pd], base

R1 R2

R1X

Stille (C-C)

R1

R2

R1
R2

Buchwald-Hartwig (C-N and/or C-O)

R2Sn(alkyl)3

[Pd]

R2
HN
R2

R1 R2

R1 = alkenyl, (hetero)aryl, acyl

R2 = alkenyl, (hetero)aryl, alkyl
X = Cl, Br, I, OTf

R1X

or
HO

R3

R1 = (hetero)aryl
R2 = 1o or 2o aryl or alkyl
R3 = 1o, 2o, or 3o alkyl, aryl
X = Cl, Br, I, OTf

References:

Negishi, E., Handbook of Organopalladium Chemistry for Organic Synthesis; John Wiley & Sons: New York, NY, 2002.
Tsuji, J., Palladium Reagents and Catalysts: New Perspectives for the 21st Century; John Wiley & Sons: Chichester, West Sussex, England, 2004.
Krti, L. and Czak, B. Strategic Applications of Named Reactions in Organic Synthesis; Elsevier Academic Press: Burlington, MA, 2005.
Li, J. J. Named Reactions for Homologations; John Wiley & Sons: Hoboken, NJ, 2009.

Aldrich.com

[Pd], Cu(I)-salt,
base

R2
R1 = alkenyl, (hetero)aryl
R2 = H, alkenyl, (hetero)aryl, alkyl, SiR3
X = Cl, Br, I, OTf

R = alkenyl, (hetero)aryl, alkyl

R2 = alkenyl, (hetero)aryl, alkynyl, alkyl
Y = alkyl, OH, O-alkyl
X = Cl, Br, I, OTf

[Pd], base

R2

Sonogashira (C-C)

R1X

R1 = alkenyl, (hetero)aryl, alkyl (w/o -hydrogens)

R2 = alkenyl, (hetero)aryl, alkyl
X = Cl, Br, I, OTf, OTs, N2+

Suzuki (C-C)
R1X

R1X

Order 800-325-3010

Technical Service 800-325-5832

[Pd], base

R2
R1 N
R2
or
R3
R1 O

H3C

[Pd(allyl)Cl]2

12012-95-2

365.89

Yellow

Air/Moisture
Sensitive

Pd(MeCN)2Cl2

14592-56-4

259.43

Dark
Orange

Air Stable

Pd(dba)2

32005-36-0

575.00

Black

Air/Moisture
Sensitive

Pd(TFA)2

42196-31-6

332.45

Brown

Air Stable

Pd2(dba)3

51364-51-3

915.72

Dark
Purple
to Black

Air Stable

Pd2(dba)3 CHCl3

52522-40-4

1035.10

Purple

Air Stable

Pd(PPh3)4

14221-01-3

1155.56

Yellow

Air/Moisture
Sensitive

Pd(OAc)2

3375-31-3

224.51

Orange- Air Stable

Brown

Pd(PCy3)2Cl2

29934-17-6

738.18

Yellow

Air Stable

Pd(PPh3)2Cl2

13965-03-2

701.90

Yellow

Air/Moisture
Sensitive

BuchwaldHartwig

Stability
Air Stable

Sonogashira

Mol. Wt. Color

304.64
Yellow

Heck

CAS No.
14024-61-4

Stille

Common Name
Pd(acac)2

Suzuki

Structure and Cat. No.

Negishi

Palladium Catalysts and Precursors

O
Pd
O

H3C

209015
CH2 Cl H2C
Pd
Pd
CH2 Cl H2C

222380
(CH3CN)2PdCl2

225657
O
Pd

227994
O
F3C

Pd2+
O

299685
O
Pd2
3

328774
O

CHCl3
Pd2
3

366315
(chloroform adduct of 328774)
Pd

P
3

216666
697265
O
H3C

Pd2+

O-

520764

Cl
Pd
Cl

403237

Cl
Pd
Cl

412740

Heck

Air Stable

Red

Air Stable

816.64

Red

Air Stable

95408-45-0

651.75

Brown

Air Stable

Pd(MeCN)4(BF4)2

21797-13-7

444.24

Dark
Yellow

Air/Moisture
Sensitive

PdBr2

13444-94-5

266.23

Dark
Brown

Air Stable

PdCl2

7647-10-1

177.33

RedBrown

Air Stable

(SPhos) palladium(II)
phenethylamine
chloride (1:1 MTBE
solvate)

N/A

760.72

White

Air-Stable

(XPhos) palladium(II)
phenethylamine
chloride

1028206-56-5

738.76

White

Air-Stable

Common Name
Pd[P(o-tol)3]2Cl2

CAS No.
40691-33-6

Mol. Wt. Color

786.06
Yellow

Stability
Air/Moisture
Sensitive

Pd(amphos)Cl2

887919-35-9

708.07

Yellow

Pd(dppf )Cl2

72287-26-4

731.70

Pd(dppf )Cl2 CH2Cl2

95464-05-4

Pd(dtbpf )Cl2

Cl

CH3
Pd

H3C

Cl

BuchwaldHartwig

Stille

CH3

Suzuki

CH3

Negishi

Structure and Cat. No.

Sonogashira

Application Guide for Palladium Catalyzed Cross-Coupling Reactions

H3C

H3C

453048
t-Bu Cl
P
Pd
t-Bu Cl

H3C
N
H3C

t-Bu
P
t-Bu

CH3
N
CH3

678740
Ph
P Ph
PdCl2

Fe
P Ph
Ph

697230
Ph
P Ph
CH2Cl2

PdCl2

Fe

P Ph
Ph

379670
t-Bu t-Bu
P
Fe

PdCl2
P
t-Bu t-Bu

701602
Pd(CH3CN)4(BF4)2

339768

PdBr2

205877

PdCl2

520659

NH2
Pd Cl

CH3O

t-Bu OCH3

NEW
OCH3

704946
Pd

NH2
Cl

i-Pr

NEW

P
i-Pr

i-Pr

704954

NH2
Pd Cl

i-Pr O

BuchwaldHartwig

Heck

Stille

Suzuki

Structure and Cat. No.

Negishi

Palladium Catalysts and Precursors

Sonogashira

Application Guide for Palladium Catalyzed Cross-Coupling Reactions

Common Name
CAS No.
(RuPhos) palladium(II) 1028206-60-1
phenethylamine
chloride

Mol. Wt. Color

728.68
White

Stability
Air-Stable

(t-BuXPhos)
palladium(II)
phenethylamine
chloride

1142811-12-8

686.69

White

Air-Stable

(BrettPhos)
palladium(II)
phenethylamine
chloride

1148148-01-9

798.81

White

Air Stable

Herrmanns Catalyst
or cataCXium C

172418-32-5

937.64

Light
yellow

Air Stable

Pd-PEPPSI-IPr

905459-27-0

679.46

Yellow

Air Stable

Pd-PEPPSI-SIPr

927706-57-8

681.47

Yellow

Air Stable

Pd-PEPPSI-IPent

1158652-41-5

791.67

Yellow

Air Stable

NEW
O i-Pr

707589
Pd
i-Pr

NEW

NH2
Cl

P t-Bu
i-Pr t-Bu

i-Pr

708739
Pd

NH2
Cl

P
H3CO

i-Pr
i-Pr

NEW

OCH3 i-Pr

718750
CH3
CH3

CH3
H3C

O
Pd
O

O
Pd
O

CH3

CH3

671916
i-Pr

i-Pr
N

i-Pr i-Pr
Cl Pd Cl
N
Cl

669032
i-Pr

i-Pr
N

i-Pr i-Pr
Cl Pd Cl
N
Cl

674702
H3C

CH3

H3C
N

CH3
H3C

Cl

H3C
Pd Cl
N

NEW

CH3

Cl

732117

CH3

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