BIS(ACETYLACETONATO)ZINC(II) 1

Bis(acetylacetonato)zinc(II) alcohols with the zinc enolate of β-keto esters and β-diesters as
well as other β-diketones (eq 2).1
Zn(MeCOCHCOMe)2(H2O) Zn(acac)2
R3 PdCl2(PPh3)2 (2.5 mol %) R3 O
Ti(O-i-Pr)4, LiCl
R1 (1)
[14024-63-6] C10 H16 O5 Zn (MW 263.60) R1 OH [MeO(CH2)2]2O
InChI = 1/2C5H8O2.H2O.Zn/c2*1-4(6)3-5(2)7;;/h2*3,6H,1- R2 or DME, 120 °C R2
60–85% (GC)
2H3;1H2;/q;;;+2/p-2/b2*4-3-;;/f2C5H7O2.H2O.Zn/h2*
6h;;/q2*-1;;m R1 = 2-naphthyl, R2 = R3 = H; R1 = R3 = H, R2 = Ph; R1 = R2 = H, R3 = Ph
InChIKey = KUJHAYOLESEVSA-AJSOYRIJDL
ZnCl2, Et3N
Ph OH PdCl2(PPh3)2 (2.5 mol %)
(catalyst for the coupling of aryl substituted allylic alcohols O
Ti(O-i-Pr)4, LiCl
with β-dicarbonyl compounds,1 and of organoboranes with + (2)
[MeO(CH2)2]2O Ph R2
organohalides;2 selective C-alkylation of β-diketones;3 prepa- O O or DME, 120 °C R3
ration of amino acid derivatives, aminomaleimides,4 and β- 40–55%
R1 R2
trichloromethyleneamino diones5 )
R1 = R2 = Me, R3 = H; R1= R2 = Ph, R3 = H;
Alternate Name: Zn(acac)2 . R1 = Ph, R2 = OEt, R3 = H; R1 = R2 = OEt, R3 = CO2Et
Physical Data: mp: anhydrous: 127 ◦ C; monohydrate: 135–
138 ◦ C. Unsymmetrical ketones are produced through the carbonyla-
Solubility: dissolves readily in most organic solvents. tive cross-coupling reaction of aryl iodides or benzyl halides
Form Supplied in: crystalline; widely available. with trialkylboranes mediated by Zn(acac)2 and PdCl2 (PPh3 )2 .
Preparative Method: from the reaction of ZnSO4 ·7H2 O with Typically, yields for this coupling process range from 43–82%.2
acetylacetone (2,4-pentanedione) and NaOH.6 The use of either Et3 B or B-alkyl-9BBN derivatives proved to be
Purification: anhydrous: sublimation, 110 ◦ C (0.1 mmHg), efficient in the transfer of the desired alkyl group (eq 3).2 For
recrystallized from n-hexane;6 monohydrate: recrystallized activation of these coupling reactions, Zn(acac)2 is superior to the
from ethyl acetate.6 acetoacetonate complexes of various other metals (i.e. Li, Mg, Al,
Handling, Storage, and Precautions: hygroscopic; irritating to Ca, Ti, Mn, Fe, Co, Cu, Mo, and Sn).
eyes, respiratory system and skin. The monohydrate is unstable
toward heat, and forms byproducts on dissolution of the hydrate. Zn(acac)2
PdCl2(PPh3)2 (2.5 mol %) O
The anhydrous zinc complex is stable toward heat. R1X + R2BBN + CO (3)
THF/HMPA (4:1), 50–55 °C R1 R2

R1X = PhI, PhCH2Cl; R2 = primary or secondary alkyl

Introduction. Zn(acac)2 is a widely available catalyst which
is prepared through the reaction of ZnSO4 , acetylacetone and Selective C-alkylation occurs through the addition of vari-
NaOH, to give either the hydrate or the anhydrous zinc complex.5 ous SN 1-type organohalides to the nucleophilic carbon of the
Zn(acac)2 can perform two general types of reactions: (1) stoi- Zn(acac)2 (eq 4).3 This transformation provides yields compa-
chiometric reaction at the nucleophilic carbon of the zinc acety- rable to those obtained with Co(acac)2 , but overall these reagents
lacetonate, and (2) catalytic reaction at the nucleophilic carbon are less effective than Co(acac)3 .3
of other β-dicarbonyl substrates.
O CHCl3 O
Stoichiometric Coupling Reactions. Zn(acac)2 efficiently Zn/n + RX R (4)
reflux, 17 h
forms a carbon–carbon bond through the coupling of aryl sub- O O
stituted allylic alcohols with the nucleophilic central carbon of
the acetoacetonate ligand (eq 1).1 Starting with either (E) or RX = PhCH2Br, PhCH(Me)Br, Ph2CHBr, Ph3CCl, 1-bromoadamantane
(Z) allylic alcohols, these reactions give (E)-γ,δ-unsaturated ke-
tones through syn–anti isomerization of the intermediate π-allyl
palladium species. The Titanium Tetraisopropoxide serves to Catalytic Reactions with β-Dicarbonyl Compounds.
(1) activate the allylic alcohol toward π-allyl complex forma- Unsaturated α-amino acid derivatives are obtained through the
tion via an allyl titanate, and (2) activate the coupled dicarbonyl Zn(acac)2 catalyzed reaction of ethyl cyanoformate with β-
species toward deacylation. An intractable mixture of products diketones, β-keto esters, and β-diesters (eq 5).4 Similar reactions
occurs when alkyl rather than aryl substituted allylic alcohols are with β-keto amides result in the formation of cyclic aminoma-
used.1 Of the various palladium catalysts investigated for this leimides (eq 6).4
reaction, Tetrakis(triphenylphosphine)palladium(0) is effective O O
while PdCl2 , Pd(OAc)2 , and PdCl2 (PhCN)2 are not. Zn(acac)2 O O Zn(acac)2 (1 mol %)
can also be prepared in situ by mixing Zinc Chloride and acety- + NCCO2Et R1 R2 (5)
CH2Cl2
lacetone in the presence of Triethylamine, and can then be used R1 R2
73–96% H2N CO2Et
to perform transformations similar to those previously described.
This in situ preparation can also be employed to couple allylic R1 = R2 = Me; R1 = R2 = Ph; R1 = Me, R2 = OEt; R1 = R2 = OEt

Avoid Skin Contact with All Reagents

2 BIS(ACETYLACETONATO)ZINC(II)

O O H2N COMe 1. Itoh, K.; Hamaguchi, N.; Miura, M.; Nomura, M., J. Chem. Soc., Perkin
Zn(acac)2 (1 mol %)
+ NCCO2Et (6) Trans. 1 1992, 2833.
NHR CH2Cl2
O N O 2. Wakita, Y.; Yasunaga, T.; Akita, M.; Kojima, M., J. Organomet. Chem.
R = H, 52%; R = Bn, 90% R 1986, 301, C17.
3. González, A.; Güell, F.; Marquet, J.; Moreno-Mañas, M., Tetrahedron
Zn(acac)2 also effectively promotes the addition of β-diketones Lett. 1985, 26, 3735.
or β-keto esters to trichloroacetonitrile, giving β-trichloromethyl- 4. Veronese, A. C.; Gandolfi, V.; Longato, B.; Corain, B.; Basato, M., J. Mol.
eneamino diones in 40–90% yields.5 The addition of β-dicarbonyl Catal. 1989, 54, 73.
compounds to cyanogen can be achieved with the use of either 5. Veronese, A. C.; Talmelli, C.; Gandolfi, V.; Corain, B.; Dasato, M., J. Mol.
Cu(acac)2 or Zn(acac)2 (eq 7). These metal catalyzed reactions of Catal. 1986, 34, 195.
cyanogen with β-keto amides give different regioselectivity when 6. Rudolph, G.; Henry, M. C., Inorg. Synth. 1967, 10, 74.
compared to catalysis by the ethoxide ion.7 7. (a) Basato, M.; Campostrini, R.; Corain, B.; D’Angeli, F.; Veronese, A.
C.; Valle, G., Inorg. Chim. Acta 1985, 98, L17. (b) Corain, B.; Basato, M.;
O O Marcomini, A.; Klein, H.-F., Inorg. Chim. Acta 1983, 74, 1. (c) Corain,
O O Zn(acac)2 (1 mol %) B.; Basato, M.; Mori, E.; Valle, G., Inorg. Chim. Acta 1983, 76, L277.
+ NC-CN t-Bu t-Bu (7)
toluene, rt
t-Bu t-Bu
50% NC NH2 Nancy S. Barta & John R. Stille
Michigan State University, East Lansing, MI, USA

A list of General Abbreviations appears on the front Endpapers