PHENYLZINC CHLORIDE

1

Phenylzinc Chloride

PhZnCl

[28557-00-8]

C

6

H

5

ClZn

(MW 177.95)

InChI = 1/C6H5.ClH.Zn/c1-2-4-6-5-3-1;;/h1-5H;1H;/q;;+1/p-

1/fC6H5.Cl.Zn/h;1h;/q;-1;m/rC6H5ClZn/c7-8-6-4-2-1-
3-5-6/h1-5H

InChIKey = VFHDCDDYMMQCBF-PIZJLVLPCC

(phenyl coupling reagent in the presence of palladium(0) or

copper(I) complexes)

Solubility:

sol ether, THF; reacts rapidly with H

2

O and protic

solvents.

Preparative Methods:

usually prepared by transmetalation of

Phenylmagnesium Bromide with Zinc Chloride.

1

Related

arylzinc halides can either be prepared by the direct inser-
tion of zinc,

2

by a transmetalation from the corresponding

aryllithium,

3

or electrochemically.

4

Diarylzincs have been gen-

erated under Barbier conditions.

5

Handling, Storage, and Precautions:

reacts with oxygen; should

be handled and stored under an inert atmosphere in the absence
of moisture.

Palladium- and Nickel-catalyzed Reactions.

Although

arylzinc halides display a low reactivity toward many organic
electrophiles, the use of late transition metal (Ni, Pd) complexes
allows cross-coupling reactions to be performed with a variety of
electrophiles. In pioneering work by Negishi,

1

,

6

the coupling of

phenylzinc chloride with various aromatic, allenic, and alkenyl

7

iodides or bromides in the presence of 1–5 mol % of a Pd

0

catalyst

provides a unique preparation of polyfunctionalized unsaturated
molecules (eqs 1 and 2).

8

,

9

Cross coupling with alkenyl triflates

is also possible (eq 3).

10

Cl

Cl

H

CO

2

Et

H

Ph

Cl

H

CO

2

Et

H

PhZnCl

1 mol % PdCl

2

L

2

(1)

86%

Et

Ph

TMS

Br

Et

Ph

TMS

Ph

PhZnCl, THF
cat Pd(PPh

3

)

4

(2)

95%

TfO

O

OMe

Ph

O

OMe

PhZnCl, THF
cat Pd(PPh

3

)

4

(3)

97%

The Pd-catalyzed reaction of phenylzinc chloride with acid

chlorides gives an efficient preparation of various types of ke-
tones (eq 4).

11

The Ni-catalyzed coupling of α-bromo nitriles and

esters furnishes the arylated carbonyl derivatives in satisfactory
yields.

12

The Pd-catalyzed substitution with allylic acetates pro-

ceeds at the more hindered position of the allylic system, whereas
the substitution reaction with stabilized nucleophiles occurs at
the less hindered position (eq 5).

13

Also, contrary to the reac-

tion with stabilized nucleophiles, the substitution with phenyl-

zinc chloride always proceeds with formal inversion (eq 6).

14

1-Vinylcyclopropyl tosylate reacts with high regioselectivity with
phenylzinc chloride.

15

An intramolecular carbopalladation of

alkynes triggered by anoxidative addition of a phenylpalladium
complex to aromatic iodides provides an interesting synthesis of
various cyclic systems (eq 7).

16

Finally, diphenylzinc undergoes a

1,4-addition to unsaturated aldehydes and ketones in the presence
of a nickel catalyst.

5

PhZnCl, THF
cat Pd(PPh

3

)

4

(4)

Cl

O

Ph

O

92%

PhZnCl, THF
cat Pd(PPh

3

)

4

(5)

OAc

Pr

Ph

Pr

Pr

Ph

+

1:99

71%

PhZnCl, THF
cat Pd(PPh

3

)

4

(6)

CO

2

H

Ph

O

O

94%

PhZnCl, THF
cat Pd(PPh

3

)

4

(7)

N

I

Ac

N

Ac

Ph

60%

Copper-mediated Reactions. Transmetalation of phenylzinc

halides to the corresponding copper reagents allows the reaction
with allylic halides, enones, and acid chlorides in satisfactory
yields (eq 8).

2

(8)

O

Ph

1. CuCN•2LiCl
2. cyclohexenone
TMSCl

PhZnI

3. H

2

O

93%

1.

Negishi, E.; Takahashi, T.; King, A. O., Org. Synth. 1988, 66, 67.

2.

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3.

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4.

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5.

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1985, 26, 829.

6.

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22

, 2715.

7.

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Avoid Skin Contact with All Reagents

2

PHENYLZINC CHLORIDE

(c) Minato, A.; Suzuki, K.; Tamao, K., J. Am. Chem. Soc. 1987, 109,
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23

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8.

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9.

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10.

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11.

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1983, 24, 5181.

12.

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13.

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22

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14.

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16.

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Paul Knochel

Philipps-Universität Marburg, Marburg, Germany

A list of General Abbreviations appears on the front Endpapers