Synthesis, Structural Characterization, and Application in Negishi

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1,3-Butadienylzinc Trimer Formed via Transmetalation from 1,4Dilithio-1,3-butadienes: Synthesis, Structural Characterization, and Application in Negishi Cross-Coupling Yi Zhou,† Wen-Xiong Zhang,† and Zhenfeng Xi*,†,‡ †

Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, People's Republic of China ‡ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry (SIOC), CAS, Shanghai 200032, People's Republic of China S Supporting Information *

ABSTRACT: The first well-defined 1,3-butadienylzinc trimers have been synthesized by transmetalation of 1,4dilithio-1,3-butadienes with 1 equiv of ZnBr2. Their structures have been determined by single-crystal X-ray structural analysis. Their reaction chemistry has been demonstrated by Pd-catalyzed Negishi cross-coupling with iodobenzenes.

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provide 2f in 95% isolated yield (Table 1, entry 6). The reaction of 2,2′-dilithiobiphenyl 1g with ZnBr2 gave rise to the o-biphenylenezinc trimer 2g (Table 1, entry 7).8 It should be noted that the same complexes 2 were obtained as sole products even with an excess amount of ZnBr2. These 1,3butadienylzinc trimers 2a−g are all stable under an N2 atmosphere even at 100 °C and are soluble in common solvents, such as hexane, benzene, and THF. 1,3-Butadienylzinc trimers 2a−c were structurally characterized by X-ray single-crystal structural analyses (Figure 1, 2a,c; see the Supporting Information for details), in the triclinic P1,̅ hexagonal P6522, and monoclinic C2/c space groups, respectively. They all exhibit a novel trimeric 1,3-butadienezinc pattern in their solid state, independent of the substituents on the 1,3-butadienyl skeleton. These results are in marked contrast with their precursors 1,4-dilithio-1,3-butadienes, the structures of which are dependent on their substituents.5,9 Three 1,3-butadienylzinc “CCCCZn” units comprise a 15membered metallacycle. Each zinc atom is supported by two σbonded 1,3-butadiene units. The distances between two zinc centers ranged from 2.8440(6) to 2.9255(6) Å in 2a and 3.203 to 3.233 Å in 2c, which are much longer than the Zn−Zn metal bond in the reported Cp*Zn−ZnCp*,10 indicating the absence of Zn−Zn bonds. The Zn−C bond lengths in 2a,c (1.939(3)− 1.976(5) Å) were both comparable with the reported C(sp2)− Zn−C(sp2) bonds in Zn[C(H)CMe2]2 (1.987(9)−2.006(7) Å).4 The C−Zn−C bond angles between the vinyl σ bonds in 2a,c fall between 172.66(13)−177.52(13) and 163.8(2)− 167.0(2)°, exhibiting a small difference due to the steric effects

rganozinc compounds are useful synthetic reagents and readily available reactive organometallic intermediates.1 There are many reports on their reactivities and synthetic applications. In contrast, much less investigation has been carried out on their structures.2−4 Walsh and co-workers reported the structure of the divinylzinc complex Zn[C(R) CH2]2, which features four-coordinated zinc centers with two σ-bonded vinyl groups and two π interactions with the neighboring divinylzinc units.4 We have been interested in the reaction chemistry and transmetalation of 1,4-dilithio-1,3-butadienes (1).5,6 Our previous results demonstrated that those organo-dimetallic compounds formed via this transmetalation show unique structures and reactivities.6 Herein we report the synthesis, structural characterization, and reaction chemistry of the first well-defined 1,3-butadienylzinc trimers (2) formed from 1,4dilithio-1,3-butadienes (1) and ZnBr2. Although there are many metalloles,7 to our knowledge, these are the first well-defined trimetallic organozinc macrocycles.8

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RESULTS AND DISCUSSION 1,2,3,4-Tetramethyl-substituted 1,4-dilithio-1,3-butadiene (1a) in Et2O was generated in situ from its corresponding 1,4diiodo-1,3-butadiene and 4 equiv of tBuLi.5 After 1 equiv of ZnBr2 in Et2O was added at 0 °C, the resulting solution was warmed to room temperature for 30 min. The pure salt-free product 2a was obtained in 84% yield via recrystallization in hexane at −20 °C (Table 1, entry 1). Similar to the case for 2a, when 1b−e were treated with ZnBr2, their corresponding 1,3butadienylzinctrimers 2b−e were produced in excellent isolated yields (Table 1, entries 2−5). The unsymmetric 1,4-dilithio-1,3butadiene 1f could be also applied to the present conditions to © 2012 American Chemical Society

Received: June 8, 2012 Published: July 16, 2012 5546

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monophenylated product 3a in toluene at 90 °C in 88% isolated yield upon hydrolysis. The expected double crosscoupling product was not observed, even with a large excess of iodobenzene and at higher temperatures. When the reaction mixture was quenched with D2O, the D-incorporated product 3a-D was isolated in 91% yield (>95% D). These results indicate that one Zn−C bond remains but is inert toward a second cross-coupling with iodobenzene, probably due to the butadienyl conjugation. In contrast, when 1,2-diiodobenzene was used, the aromatization product 1,2,3,4-tetraethylnaphthalene (5) was obtained in 89% isolated yield,12 probably owing to the aromatization driving force that makes the second intramolecular Negishi cross-coupling take place. In summary, the first well-defined 1,3-butadienylzinc trimer compounds 2 having a 15-membered metallacyclic ring with 3 zinc centers have been achieved by transmetalation of 1,4dilithio-1,3-butadienes (1) with 1 equiv of ZnBr2. Preliminary results indicate that these macrocyclic organozinc compounds should have interesting and useful reactivity and synthetic applications.

Table 1. Formation of 1,3-Butadienylzinc Trimers 2 via Transmetalation of 1,4-Dilithio-1,3-butadienes 1 with ZnBr2

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EXPERIMENTAL SECTION

General Procedures. All reactions were carried out under a slightly positive pressure of dry and oxygen-free nitrogen by using standard Schlenk line techniques or under a nitrogen atmosphere in a glovebox. The nitrogen in the glovebox was constantly circulated through a copper/molecular sieves catalyst unit. The oxygen and moisture concentrations in the glovebox atmosphere were monitored to ensure both were always below 1 ppm. Unless otherwise noted, all starting materials were commercially available and were used without further purification. Solvent was distilled from sodium/benzophenone under a nitrogen atmosphere. 1H NMR and 13C NMR spectra were recorded on a JEOL-AL300 spectrometer (FT, 300 MHz for 1H; 75 MHz for 13C), a Bruker-400 spectrometer (FT, 400 MHz for 1H; 100 MHz for 13C), and a Bruker-500 spectrometer (FT, 500 MHz for 1H; 125 MHz for 13C) at room temperature. Organometallic samples for NMR spectroscopic measurements were prepared in the glovebox by use of J. Young valve NMR tubes (Wilmad 528-JY). Synthesis of 1,3-Butadienylzinc Trimer. A solution of substituted 1,4-diiodo-1,3-butadiene (1 mmol) in Et2O (10 mL) was cooled to −78 °C, and tBuLi (4 mmol, 1.6 M in pentane) was added dropwise. The reaction mixture was then stirred at −78 °C for 1 h, and 1,4-dilithio-1,3-butadiene 1 (1 mmol) was generated in situ. The reaction mixture was warmed to 0 °C, anhydrous ZnBr2 (1 mmol) dissolved in Et2O was added, and then the resulting solution was stirred at room temperature for 30 min. The pure salt-free product 2 was obtained by extraction with hexane and recrystallization in hexane at −20 °C. 2a: colorless solid, isolated yield 84%; 1H NMR (400 MHz, C6D6, Me4Si) δ 1.82 (s, 18 H, 6 CH3), 1.90 (s, 18 H, 6 CH3); 13C NMR (100 MHz, C6D6, Me4Si) δ 15.45 (s, 6 CH3), 21.01 (s, 6 CH3), 147.93 (s, 6 quat C), 159.52 (s, 6 quat C). Anal. Calcd for C24H36Zn3: C, 55.35; H, 6.97. Found: C, 55.52; H, 7.02. Recrystallization of 2a from hexane at −20 °C gave crystals suitable for X-ray analysis. 2b: colorless solid, isolated yield 92%; 1H NMR (500 MHz, C6D6) δ 1.01−1.05 (m, 36 H, 12 CH3), 2.02−2.18 (m, 12 H, 6 CH2), 2.41− 2.51 (m, 12 H, 6 CH2); 13C NMR (75 MHz, C6D6) δ 13.34 (s, 6 CH3), 17.24 (s, 6 CH3), 22.04 (s, 6 CH2), 27.76 (s, 6 CH2), 157.73 (s, 6 quat C), 161.96 (s, 6 quat C). Anal. Calcd for C36H60Zn3: C, 62.75; H, 8.78. Found: C, 62.71; H, 8.64. Recrystallization of 2b from hexane at −20 °C gave crystals suitable for X-ray analysis. 2c: colorless solid, isolated yield 95%; 1H NMR (300 MHz, C6D6) δ 0.18 (s, 54 H, 18 CH3), 1.97 (s, 18 H, 6 CH3); 13C NMR (75 MHz, C6D6) δ 1.84 (s, 18 CH3), 24.51 (s, 6 CH3), 148.55 (s, 6 quat C), 174.33 (s, 6 quat C). Anal. Calcd for C36H72Si6Zn3: C, 49.72; H, 8.34. Found: C, 49.77; H, 8.37. Recrystallization of 2c from hexane at −20 °C gave crystals suitable for X-ray analysis.

Isolated yields. bConditions: −78 °C for 15 min then room temperature for 30 min.

a

of bulky substituents. However, these angles are much larger than those found in Zn[C(Me)CH 2 ] 2 (132.4(3)− 139.4(3)°).4 The reaction chemistry of such macrocyclic organozinc compounds was demonstrated by the Pd-catalyzed Negishi cross-coupling with iodobenzenes.11 As shown in Scheme 1, the reaction between 2b and iodobenzene gave exclusively the 5547

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Figure 1. ORTEP drawings of 2a (left) and 2c (right) with 30% thermal ellipsoids. Selected bond lengths (Å) and angles (deg) for 2a: Zn(1)− C(20) = 1.936(3), Zn(1)−C(1) = 1.939(3), Zn(2)−C(4) = 1.944(3), Zn(2)−C(9) = 1.945(3), Zn(3)−C(12) = 1.933(3), Zn(3)−C(17) = 1.936(3), Zn(1)−Zn(2) = 2.9255(6), Zn(1)−Zn(3) = 2.8440(6), Zn(2)−Zn(3) = 2.9101(7); C(20)−Zn(1)−C(1) = 172.66(13), C(4)−Zn(2)− C(9) = 177.52(13), C(12)−Zn(3)−C(17) = 172.08(13). Selected bond lengths (Å) and angles (deg) for 2c: Zn(1)−C(1) = 1.948(6), Zn(1)− C(12) = 1.951(6), Zn(2)−C(8) = 1.961(5), Zn(2)−C(9) = 1.976(5), Zn(3)−C(4) = 1.933(5), Zn(3)−C(5) = 1.948(5), Zn(1)−Zn(2) = 3.225, Zn(1)−Zn(3) = 3.203, Zn(2)−Zn(3) = 3.233; C(1)−Zn(1)−C(12) = 164.6(2), C(8)−Zn(2)−C(9) = 167.0(2), C(4)−Zn(3)−C(5) = 163.8(2). 2g: colorless solid, isolated yield 65%; 1H NMR (500 MHz, C6D6, Me4Si) δ 6.81−6.85 (m, 6 H, 6 CH), 6.89−6.92 (m, 6 H, 6 CH), 7.14−7.16 (m, 12 H, 12 CH); 13C NMR (75 MHz, C6D6) δ 127.42 (s, 6 CH), 127.45 (s, 6 CH), 128.46 (s, 6 CH), 129.00 (s, 6 CH), 129.01 (s, 6 quat C), 141.67 (s, 6 quat C). Anal. Calcd for C36H24Zn3: C, 66.23; H, 3.71. Found: C, 66.21; H, 3.67. Pd-Catalyzed Negishi Cross-Coupling Reaction of 2b with Iodobenzene or 1,2-Diiodobenzene. Under nitrogen, a mixture of 1,3-butadienylzinc trimer 2b (0.5 mmol), iodobenzene or 1,2diiodobenzene (0.5 mmol), and Pd(PPh3)4 (5 mol %) in 2 mL of toluene was stirred at 90 °C (for iodobenzene) or 100 °C (for 1,2diiodobenzene) for 1 h. The reaction mixture was quenched with water and extracted with Et2O. The extraction was washed with brine and dried over MgSO4. The solvent was then evaporated under vacuum, and the residue was purified by column chromatography to give products 3a and 4. 3a: colorless liquid, isolated yield 88%; 1H NMR (500 MHz, CDCl3, SiMe4) δ 0.62 (t, J = 9.4 Hz, 3 H, 1 CH3), 0.86 (t, J = 9.5 Hz, 3 H, 1 CH3), 0.91 (t, J = 9.4 Hz, 3 H, 1 CH3), 1.00 (t, J = 9.4 Hz, 3 H, 1 CH3), 1.75−1.90 (m, 4 H, 2 CH2), 2.25 (q, J = 9.4 Hz, 2 H, 1 CH2), 2.40 (q, J = 9.3 Hz, 2 H, 1 CH2), 4.91 (t, J = 9.2 Hz, 1 H, 1 CH), 7.06−7.19 (m, 5 H, 5 CH); 13C NMR (75 MHz, CDCl3, SiMe4) δ 13.34 (s, 1 CH3), 13.37 (s, 1 CH3), 13.45 (s, 1 CH3), 13.92 (s, 1 CH3), 20.99 (s, 1 CH2), 22.81 (s, 1 CH2), 24.49 (s, 1 CH2), 27.30 (s, 1 CH2), 125.23 (s, 1 CH), 127.16 (s, 2 CH), 129.53 (s, 2 CH), 132.24 (s, 1 CH), 137.30 (s, 1 quat C), 139.71 (s, 1 quat C), 141.16 (s, 1 quat C), 144.40 (s, 1 quat C).13 3a-D: colorless liquid, isolated yield 91%; 1H NMR (400 MHz, CDCl3, SiMe4) δ 0.62 (t, J = 9.4 Hz, 3 H, 1 CH3), 0.86 (t, J = 9.5 Hz, 3 H, 1 CH3), 0.91 (t, J = 9.4 Hz, 3 H, 1 CH3), 1.00 (t, J = 9.4 Hz, 3 H, 1 CH3), 1.80−1.88 (m, 4 H, 2 CH2), 2.25 (q, J = 9.4 Hz, 2 H, 1 CH2), 2.40 (q, J = 9.3 Hz, 2 H, 1 CH2), 7.06−7.19 (m, 5 H, 5 CH); 13C NMR (100 MHz, CDCl3, SiMe4) δ 13.31 (s, 1 CH3), 13.35 (s, 1 CH3), 13.45 (s, 1 CH3), 13.89 (s, 1 CH3), 20.91 (s, 1 CH2), 22.82 (s, 1 CH2), 24.53 (s, 1 CH2), 27.30 (s, 1 CH2), 125.26 (s, 1 CH), 127.18 (s, 2 CH), 129.54 (s, 2 CH), 131.88 (t, JC‑D = 22.9 Hz, 1 CD), 137.37 (s, 1 quat C), 139.67 (s, 1 quat C), 141.19 (s, 1 quat C), 144.43 (s, 1 quat C); HRMS (ESI) calcd for C18H25D [M + H]+ 244.2171, found 244.2170. 4: colorless liquid, isolated yield 89%; 1H NMR (400 MHz, CDCl3, SiMe4) δ 1.25 (t, J = 7.4 Hz, 6 H, 2 CH3), 1.31 (t, J = 7.5 Hz, 6 H, 2 CH3), 2.85 (q, J = 7.4 Hz, 4 H, 2 CH2), 3.11 (q, J = 7.4 Hz, 4 H, 2 CH2), 7.40−7.42 (m, 2 H, 2 CH), 8.02−8.04 (m, 2 H, 2 CH); 13C NMR (100 MHz, CDCl3, SiMe4) δ 15.53 (s, 2 CH3), 15.86 (s, 2 CH3), 21.71 (s, 2 CH2), 22.78 (s, 2 CH2), 124.49, 124.53 (s, 2 quat C), 131.01 (s, 2 quat C), 135.38 (s, 2 quat C), 137.75 (s, 2 quat C).12a

Scheme 1. Pd-Catalyzed Negishi Cross-Coupling of 1,3Butadienylzinc Trimer 2b with Iodobenzenes

2d: colorless solid, isolated yield 92%; 1H NMR (300 MHz, C6D6, Me4Si) δ 0.32 (s, 54 H, 18 CH3), 7.61−7.86 (m, 30 H, 30 CH); 13C NMR (75 MHz, C6D6) δ −0.19 (s, 18 CH3), 127.43 (s, 6 CH), 128.07 (s, 12 CH), 130.23 (s, 12 CH), 134.45 (s, 6 quat C), 142.57 (s, 6 quat C), 160.69 (s, 6 quat C). Anal. Calcd for C66H84Si6Zn3: C, 63.82; H, 6.82. Found: C, 63.69; H, 6.74. 2e: colorless solid, isolated yield 72%; 1H NMR (500 MHz, THFD8) δ −0.13 (s, 36 H, 12 CH3), 7.26−7.37 (m, 60 H, 60 CH); 13C NMR (75 MHz, THF-D8) δ −0.23 (s, 12 CH3), 93.87 (s, 6 quat C), 106.31 (s, 6 quat C), 124.25 (s, 6 quat C), 128.36 (s, 6 CH), 128.69 (s, 12 CH), 129.00 (s, 12 CH), 129.29 (s, 6 CH), 130.88 (s, 12 CH), 131.82 (s, 6 quat C), 132.57 (s, 12 CH), 142.19 (s, 6 quat C), 162.26 (s, 6 quat C). Anal. Calcd for C108H96Si6Zn3: C, 73.76; H, 5.50. Found: C, 73.83; H, 5.55. 2f: colorless liquid, isolated yield 95%; 1H NMR (500 MHz, C6D6, SiMe4) δ 0.10 (s, 27 H, 9 CH3), 0.80 (t, J = 7.4 Hz, 9 H, 3 CH3), 1.22−1.29 (m, 6 H, 3 CH2), 1.49−1.55 (m, 6 H, 3 CH2), 2.36 (t, J = 8.0 Hz, 6 H, 3 CH2), 6.75−6.88 (m, 15 H, 15 CH), 6.96−7.04 (m, 15 H, 15 CH); 13C NMR (100 MHz, THF-D8) δ 0.54 (s, 9 CH3), 14.46 (s, 3 CH3), 23.79 (s, 3 CH2), 32.96 (s, 3 CH2), 34.43 (s, 3 CH2), 127.29 (s, 3 CH), 127.87 (s, 3 CH), 128.01 (s, 3 quat C), 128.49 (s, 6 CH), 129.20 (s, 6 CH), 130.41 (s, 6 CH), 130.55 (s, 3 quat C), 130.77 (s, 6 CH), 138.37 (s, 3 quat C), 140.91 (s, 3 quat C), 146.64 (s, 3 quat C), 161.28 (s, 3 quat C). Anal. Calcd for C69H84Si3Zn3: C, 69.41; H, 7.09. Found: C, 69.43; H, 7.11. 5548

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X-ray Crystallographic Studies. Single crystals of 2a−c suitable for X-ray analysis were grown in hexane at −20 °C for 24 h. The crystals of 2a−c were manipulated under a nitrogen atmosphere and were sealed in a thin-walled glass capillary. Data collections for 2a,b were performed at −100 °C on a Rigaku CCD Saturn 724 diffractometer, using graphite-monochromated Mo Kα radiation (λ = 0.710 73 Å). Data collections for 2c were performed at 20 °C on a Rigaku RAXIS RAPID IP diffractometer, using graphite-monochromated Mo Kα radiation (λ = 0.710 73 Å). The determination of crystal class and unit cell parameters was carried out by the CrystalClear program (Rigaku Inc., 2007) for 2a,b or Rapid-AUTO program package (Rigaku Inc., 2000) for 2c. The raw frame data were processed using Crystal Clear for 2a,b or Crystal Structure (Rigaku/ MSC, 2000) for 2c to yield the reflection data file. The structures of 2a−c were solved by use of the SHELXTL program. Refinement was performed on F2 anisotropically for all the non-hydrogen atoms by the full-matrix least-squares method. The hydrogen atoms were placed at calculated positions and were included in the structure calculation without further refinement of the parameters. Crystallographic data (excluding structure factors) have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC-884573 (2a), CCDC-884574 (2b), and CCDC-884575 (2c). These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/ cif. Crystallographic data for 2a: C24H36Zn3, triclinic, space group P1̅, a = 9.7112(16) Å, b = 9.9467(14) Å, c = 13.852(2) Å, α = 70.142(8)°, β = 77.515(9)°, γ = 75.018(8)°, U = 1203.5(3) Å3, Dc = 1.437 Mg m−3, Z = 2, T = 173(2) K, colorless block, 0.34 × 0.28 × 0.23 mm3. Data collection was carried out at −100 °C on a diffractometer; 8459 reflections were collected, with 4189 independent reflections (R(int) = 0.0337), giving R1 = 0.0356 for observed unique reflections (F2 > 2σ(F2)) and wR2 = 0.0850 for all data. The maximum and minimum residual electron densities on the final difference Fourier map were 0.484 and −0.381 e Å−3. Crystallographic data for 2b: C36H60Zn3, hexagonal, space group P6522, a = 11.557(4) Å, b = 11.557(4) Å, c = 48.530(19) Å, α = 90°, β = 90°, γ = 120°, U = 5614(4) Å3, Dc = 1.223 Mg m−3, Z = 6, T = 173(2) K, colorless block, 0.35 × 0.30 × 0.28 mm3. Data collection was carried out at −100 °C on a diffractometer; 14 890 reflections were collected, with 3376 independent reflections (R(int) = 0.0464), giving R1 = 0.0461 for observed unique reflections (F2 > 2σ(F2)) and wR2 = 0.0951 for all data. The maximum and minimum residual electron densities on the final difference Fourier map were 0.295 and −0.262 e Å−3. Crystallographic data for 2c: C36H72Si6Zn3·1/2C6H14, monoclinic, space group C2/c, a = 20.106(4) Å, b = 13.786(3) Å, c = 38.576(8) Å, α = 90°, β = 95.04(3)°, γ = 90°, U = 10651(4) Å3, Dc = 1.138 Mg m−3, Z = 8, T = 293(2) K, colorless block, 0.20 × 0.20 × 0.10 mm3. Data collection was carried out at room temperature on a diffractometer; 22 920 reflections were collected, with 12 197 independent reflections (R(int) = 0.0846), giving R1 = 0.0415 for observed unique reflections (F2 > 2σ(F2)) and wR2 = 0.0612 for all data. The maximum and minimum residual electron densities on the final difference Fourier map were 0.493 and −0.515 e Å−3.

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Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the Natural Science Foundation of China and the Major State Basic Research Development Program (2011CB808700).

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ASSOCIATED CONTENT

S Supporting Information *

CIF files, figures, and tables giving crystallographic data for 2a− c and figures giving NMR spectra for all new compounds. This material is available free of charge via the Internet at http:// pubs.acs.org.

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REFERENCES

(1) For reviews on reactions of organozinc reagents, see: (a) Knochel, P.; Almena, J.; Jones, P. Tetrahedron 1998, 54, 8275−8319. (b) Boudier, A.; Bromm, L. O.; Lotz, M.; Knochel, P. Angew. Chem., Int. Ed. 2000, 39, 4415−4435. (c) Corbet, J.-P.; Mignani, G. Chem. Rev. 2006, 106, 2651−2710. (d) Rudolph, A.; Lautens, M. Angew. Chem., Int. Ed. 2009, 48, 2656−2670. (e) Yu, D.; Li, B.; Shi, Z. Acc. Chem. Res. 2010, 43, 1486−1495. (f) Jana, R.; Pathak, T. P.; Sigman, M. S. Chem. Rev. 2011, 111, 1417−1492. (2) For reports on structures of zincates, see: (a) Tochtermann, W. Angew. Chem., Int. Ed. 1966, 5, 351−371. (b) Uchiyama, M.; Matsumoto, Y.; Nobuto, D.; Furuyama, T.; Yamaguchi, K.; Morokuma, K. J. Am. Chem. Soc. 2006, 128, 8748−8750. (c) Mulvey, R. E.; Mongin, F.; Uchiyama, M.; Kondo, Y. Angew. Chem., Int. Ed. 2007, 46, 3802−3824. (d) Merkel, S.; Stern, D.; Stalke, D. Angew. Chem., Int. Ed. 2009, 48, 6350−6353. (e) Clegg, W.; Conway, B.; Garcι ́a-Alvarez, P.; Kennedy, A. R.; Klett, J.; Mulvey, R. E.; Russo, L. Dalton Trans. 2010, 39, 62−65. (3) For reports on structures of organozinc halides, see: (a) Evans, D. F.; Maher, J. P. J. Chem. Soc. 1962, 5125−5128. (b) Dessy, R. E.; Coe, G. R. J. Org. Chem. 1963, 28, 3592−3593. (c) Evans, D. F.; Wharf, I. J. Organomet. Chem. 1966, 5, 108. (d) Boersma, J.; Noltes, J, C. Tetrahedron Lett. 1966, 14, 1521−1525. (e) Guerrero, A.; Hughes, D. L.; Bochmann, M. Organometallics 2006, 25, 1525−1527. (f) Sarazin, Y.; Wright, J. A.; Harding, D. A. J.; Martin, E.; Woodman, T. J.; Hughes, D. L.; Bochmann, M. J. Organomet. Chem. 2008, 693, 1494− 1501. (g) MacIntosh, I. S.; Sherren, C. N.; Robertson, K. N.; Masuda, J. D.; Pye, C. C.; Clyburne, J. A. C. Organometallics 2010, 29, 2063− 2068. (4) Wooten, A.; Carroll, P. J.; Maestri, A. G.; Walsh, P. J. J. Am. Chem. Soc. 2006, 128, 4624−4631. (5) Xi, Z. Acc. Chem. Res. 2010, 42, 1342−1351. (6) For examples on transmetalation reactions of 1,4-dilithio-1,3butadienes, see the following. With CuCl: (a) Wang, C.; Yuan, J.; Li, G.; Wang, Z.; Zhang, S.; Xi, Z. J. Am. Chem. Soc. 2006, 128, 4564− 4565. (b) Wang, C.; Xi, Z. Chem. Commun. 2007, 5119−5133. (c) Luo, Q.; Wang, C.; Zhang, W. -X.; Xi, Z. Chem. Commun. 2008, 1593−1595. With FeCl3 or FeCl2: (d) Li, G.; Fang, H.; Li, Z.; Xi, Z. Chin. J. Chem. 2003, 21, 219−221. (e) Li, G.; Fang, H.; Xi, Z. Tetrahedron Lett. 2003, 44, 8705−8708. With AlCl3: (f) Fang, H.; Zhao, C.; Li, G.; Xi, Z. Tetrahedron 2003, 59, 3779−3786. (7) (a) Dubac, J.; Laporterie, A.; Manuel, G. Chem. Rev. 1990, 90, 215−263. (b) Colomer, E.; Corriu, R. J. P.; Lheureux, M. Chem. Rev. 1990, 90, 265−282. (c) Gessner, V. H.; Tannacl, J. F.; Miller, A. D.; Tilley, T. D. Acc. Chem. Res. 2011, 44, 435−466. (8) For examples of the formation and reaction of polyphenylene mercurials, including an o-biphenylenemercury trimer, see: (a) Massey, A. G.; Al-Jabar, N. A. A.; Humphries, R. E.; Deacon, G. B. J. Organomet. Chem. 1986, 316, 25−39. (b) Humphries, R. E. Inorg. Chem. Acta 1988, 144, 163−169. (c) West, A. J. Annu. Rep. Prog. Chem., Sect. A 2007, 103, 240−244. A bowl-shaped nanomolecule containing a 16-atom [ZnC3]4 “anti-crown” ring formed via dizincation of 2-substituted thiophene was reported very recently; see: (d) Balloch, L.; Garden, J. A.; Kennedy, A. R.; Mulvey, R. E.; Rantanen, T.;

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Robertson, S. D.; Snieckus, V. Angew. Chem., Int. Ed. 2012, 51, 6934− 6937. (9) (a) Liu, L.; Zhang, W.-X.; Wang, C.; Wang, C. Y.; Xi, Z. Organometallics 2010, 29, 278−281. (b) Luo, Q.; Wang, C.; Gu, L.; Zhang, W.-X.; Xi, Z. Chem. Asian J. 2010, 5, 1120−1128. (10) Resa, I.; Carmona, E.; Gutierrez-Puebla, E.; Monge, A. Science 2004, 305, 1136−1138. (11) For recent reviews on the Negishi cross-coupling reaction, see: (a) Yin, L.; Liebscher, J. Chem. Rev. 2007, 107, 133−173. (b) Negishi, E.; Huang, Z.; Wang, G.; Mohan, S.; Wang, C.; Hattori, H. Acc. Chem. Res. 2008, 41, 1474−1485. (c) Negishi, E. Angew. Chem., Int. Ed. 2011, 50, 6738−6764. (12) For examples on the formation of substituted naphthalenes via metal-mediated coupling of zirconacyclopentadienes with 1,2dihaloarenes, see: (a) Takahashi, T.; Hara, R.; Nishihara, Y.; Kotora, M. J. Am. Chem. Soc. 1996, 118, 5154−5155. (b) Takahashi, T.; Li, Y.; Stepnicka, P.; Kitamura, M.; Liu, Y.; Nakajima, K.; Kotora, M. J. Am. Chem. Soc. 2002, 124, 576−582. (c) Huang, W.; Zhou, X.; Kanno, K.; Takahashi, T. Org. Lett. 2004, 6, 2429−2431. (d) Seri, T.; Qu, H.; Zhou, L.; Kanno, K.; Takahashi, T. Chem. Asian J. 2008, 3, 388−392. (e) Zhou, L.; Nakajima, K.; Kanno, K.; Takahashi, T. Tetrahedron Lett. 2009, 50, 2722−2726. (f) Ni, Y.; Nakajima, K.; Kanno, K.; Takahashi, T. Org. Lett. 2009, 11, 3702−3705. (13) Takahashi, T.; Sun, W.-H.; Xi, C.; Ubayama, H.; Xi, Z. Tetrahedron 1998, 54, 715−726.

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