PHENYLZINC CHLORIDE 1
Phenylzinc Chloride 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
PhZnCl
alkynes triggered by anoxidative addition of a phenylpalladium
complex to aromatic iodides provides an interesting synthesis of
[28557-00-8] C6H5ClZn (MW 177.95)
various cyclic systems (eq 7).16 Finally, diphenylzinc undergoes a
InChI = 1/C6H5.ClH.Zn/c1-2-4-6-5-3-1;;/h1-5H;1H;/q;;+1/p-
1,4-addition to unsaturated aldehydes and ketones in the presence
1/fC6H5.Cl.Zn/h;1h;/q;-1;m/rC6H5ClZn/c7-8-6-4-2-1-
of a nickel catalyst.5
3-5-6/h1-5H
PhZnCl, THF
InChIKey = VFHDCDDYMMQCBF-PIZJLVLPCC
O O
cat Pd(PPh3)4
(4)
Cl 92% Ph
(phenyl coupling reagent in the presence of palladium(0) or
copper(I) complexes)
Solubility: sol ether, THF; reacts rapidly with H2O and protic
PhZnCl, THF
Pr
Pr Ph
cat Pd(PPh3)4
solvents.
+ (5)
Ph
Preparative Methods: usually prepared by transmetalation of OAc 71% Pr
Phenylmagnesium Bromide with Zinc Chloride.1 Related 1:99
arylzinc halides can either be prepared by the direct inser-
tion of zinc,2 by a transmetalation from the corresponding
O
aryllithium,3 or electrochemically.4 Diarylzincs have been gen-
O CO2H
PhZnCl, THF
erated under Barbier conditions.5
cat Pd(PPh3)4
(6)
Handling, Storage, and Precautions: reacts with oxygen; should
94%
be handled and stored under an inert atmosphere in the absence
Ph
of moisture.
Ph
Palladium- and Nickel-catalyzed Reactions. Although
PhZnCl, THF
I
cat Pd(PPh3)4
arylzinc halides display a low reactivity toward many organic
(7)
electrophiles, the use of late transition metal (Ni, Pd) complexes
60%
N
N
allows cross-coupling reactions to be performed with a variety of
Ac
Ac
electrophiles. In pioneering work by Negishi,1,6 the coupling of
phenylzinc chloride with various aromatic, allenic, and alkenyl7
iodides or bromides in the presence of 1 5 mol % of a Pd0 catalyst
Copper-mediated Reactions. Transmetalation of phenylzinc
provides a unique preparation of polyfunctionalized unsaturated
halides to the corresponding copper reagents allows the reaction
molecules (eqs 1 and 2).8,9 Cross coupling with alkenyl triflates
with allylic halides, enones, and acid chlorides in satisfactory
is also possible (eq 3).10
yields (eq 8).2
PhZnCl
Cl Cl
1. CuCN" 2LiCl O
H CO2Et 1 mol % PdCl2L2 H CO2Et
2. cyclohexenone
(1)
86% Ph
Cl H H
TMSCl
PhZnI (8)
3. H2O
Ph
93%
PhZnCl, THF
Ph TMS Ph TMS
cat Pd(PPh3)4
(2)
95%
Et Br Et Ph
1. Negishi, E.; Takahashi, T.; King, A. O., Org. Synth. 1988, 66, 67.
2. (a) Majid, T. N.; Knochel, P., Tetrahedron Lett. 1990, 31, 4413. (b) Zhu,
L.; Wehmeyer, R. M.; Rieke, R. D., J. Org. Chem. 1991, 56, 1445.
PhZnCl, THF
TfO Ph
cat Pd(PPh3)4
3. (a) Tucker, C. E.; Majid, T. N.; Knochel, P., J. Am. Chem. Soc. 1992, 114,
O O (3)
3983. (b) Venegas, P.; Cahiez, G.; Tucker, C. E.; Majid, T. M.; Knochel,
97%
P., J. Chem. Soc., Chem. Commun. 1992, 1406.
OMe OMe
4. Sibille, S.; Ratovelomanana, V.; Perichon, J., J. Chem. Soc., Chem.
Commun. 1992, 283.
The Pd-catalyzed reaction of phenylzinc chloride with acid
5. (a) Luche, J. L.; Petrier, C.; Dupuy, C., Tetrahedron Lett. 1984, 25, 3463.
chlorides gives an efficient preparation of various types of ke-
(b) de Souza Barboza, J. C.; Petrier, C.; Luche, J.-L., Tetrahedron Lett.
tones (eq 4).11 The Ni-catalyzed coupling ofÄ…-bromo nitriles and
1985, 26, 829.
esters furnishes the arylated carbonyl derivatives in satisfactory
6. (a) Negishi, E.; King, A. O.; Okukado, N., J. Org. Chem. 1977, 42, 1821.
yields.12 The Pd-catalyzed substitution with allylic acetates pro-
(b) Negishi, E.; Matsushita, H.; Okukado, N., Tetrahedron Lett. 1981,
ceeds at the more hindered position of the allylic system, whereas
22, 2715.
the substitution reaction with stabilized nucleophiles occurs at
7. (a) Minato, A.; Tamao, K.; Hayashi, T.; Suzuki, K.; Kumada, M.,
the less hindered position (eq 5).13 Also, contrary to the reac-
Tetrahedron Lett. 1980, 21, 845. (b) Bumagin, N. A.; Ponomaryov,
tion with stabilized nucleophiles, the substitution with phenyl- A. B.; Beletskaya, I. P., J. Organomet. Chem. 1985, 291, 129.
Avoid Skin Contact with All Reagents
2 PHENYLZINC CHLORIDE
(c) Minato, A.; Suzuki, K.; Tamao, K., J. Am. Chem. Soc. 1987, 109, 11. Negishi, E.; Bagheri, V.; Chatterjee, S.; Luo, F.-T., Tetrahedron Lett.
1257. (d) Hyuga, S.; Chiba, Y.; Yamashina, N.; Hara, S.; Suzuki, A., 1983, 24, 5181.
Chem. Lett. 1987, 1757. (e) Hyuga, S.; Yamashina, N.; Hara, S.; Suzuki,
12. (a) Klingstedt, T.; Frejd, T., Organometallics 1983, 2, 598. (b) Frejd, T.;
A., Chem. Lett. 1988, 809. (f) Satoh, Y.; Serizawa, H.; Miyaura, N.;
Klingstedt, T., Synthesis 1987, 40.
Hara, S.; Suzuki, A., Tetrahedron Lett. 1988, 29, 1811. (g) Celebuski, J.;
13. (a) Keinan, E.; Sahei, M., J. Chem. Soc., Chem. Commun. 1984, 648.
Munro, G.; Rosenblum, M., Organometallics 1986, 5, 256. (h) Bumagin,
(b) Negishi, E.; Chatterjee, S.; Matsushita, H., Tetrahedron Lett. 1981,
N. A.; Ponmarev, A. B.; Beletskaya, I. P., Zh. Obshch. Khim. 1987,
22, 3737. (c) Chatterjee, S.; Negishi, E., J. Org. Chem. 1985, 50, 3406.
23, 1345. (i) de Graaf, W.; Boersma, J.; van Koten, G.; Elsevier, C. J.,
14. (a) Matsushita, J.; Negishi, E., J. Chem. Soc., Chem. Commun. 1982, 160.
J. Organomet. Chem. 1989, 378, 115. (j) Ruitenberg, K.; Kleijn, H.;
(b) Keinan, E.; Roth, Z., J. Org. Chem. 1983, 48, 1769. (c) Dunkerton,
Elsevier, C. J.; Meijer, J.; Vermeer, P., Tetrahedron Lett. 1981, 22, 1451.
L. V.; Serino, A. J., J. Org. Chem. 1982, 47, 2813. (d) Elsevier, C. J.;
(k) Elsevier, C. J.; Vermeer, P., J. Org. Chem. 1985, 50, 3042. (l) Elsevier,
Stehouwer, P. M.; Westmijze, H.; Vermeer, P., J. Org. Chem. 1983, 48,
C. J.; Kleijn, H.; Boersma, J.; Vermeer, P., Organometallics 1986, 5, 716.
1103. (e) Fiaud, J. C.; Aribi-Zouioueche, L., J. Organomet. Chem. 1985,
(m) Elsevier, C. J.; Kleijn, H.; Ruitenberg, K.; Vermeer, P., J. Chem. Soc.,
295, 383. (f) Fiaud, J.-C.; Legros, J.-Y., J. Org. Chem. 1987, 52, 1907.
Chem. Commun. 1983, 1529. (n) Tius, M. A.; Gomez-Galeno, J.; Zaidi,
15. (a) Stolle, A.; Salaün, J.; de Meijere, A., Synlett 1991, 327. (b) Stolle,
J. H., Tetrahedron Lett. 1988, 29, 6909. (o) Okamoto, Y.; Yoshioka, K.;
A.; Ollivier, J.; Piras, P. P.; Salaün, J.; de Meijere, A., J. Am. Chem. Soc.
Yamana, T.; Mori, H., J. Organomet. Chem. 1989, 369, 285. (p) Potter, G.
1992, 114, 4051.
A.; McCague, R., J. Org. Chem. 1990, 55, 6184. (q) Gilchrist, T.; Healy,
M. A. M., Tetrahedron Lett. 1990, 31, 5807. (r) Ennis, D. S.; Gilchrist, 16. (a) Burns, B.; Grigg, R.; Sridharan, V.; Stevenson, P.; Sukirthalingam,
T. L., Tetrahedron Lett. 1989, 30, 3735. (s) Yamashina, N.; Hyuga, S.; S.; Worakun, T., Tetrahedron Lett. 1989, 30, 1135. (b) Grigg, R.;
Hara, S.; Suzuki, A., Tetrahedron Lett. 1989, 30, 6555. Loganathan, V.; Sukirthalingam, S.; Sridharan, V., Tetrahedron Lett.
1990, 31, 6573. (c) Wang, R.-T.; Chou, F.-L.; Luo, F.-T., J. Org. Chem.
8. Minato, A., J. Org. Chem. 1991, 56, 4052.
1990, 55, 4846.
9. Miller, R. B.; Al-Hassan, M. I., J. Org. Chem. 1985, 50, 2121.
10. (a) Keenan, R. M.; Kruse, L. I., Synth. Commun. 1989, 19, 793. (b) Stork,
Paul Knochel
G.; Isaacs, R. C. A., J. Am. Chem. Soc. 1990, 112, 7399.
Philipps-Universität Marburg, Marburg, Germany
A list of General Abbreviations appears on the front Endpapers