Handbook of Functionalized Organometallics Applications in S

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FG CuCN/LiCl ZnBr 0ºC CuZnBrCN 15.4 Electrosynthesis of Compounds and their Reactivity FG ClCO2Me FG Scheme 15.22 Synthesis of functionalized 4-phenylpyridines. N N CO 2Me oxidation The electrosynthesis of aryldizinc species can also be achieved using dibromobenzenes and cobalt catalysis with moderate to excellent yields [38]. At 4 F mol ±1 , only the dizinc species is obtained (Eq. (19)). However, analysis of the solution after consumption of 2F/mol of ArX 2 shows the formation of a mixture of mono (Br-Ar-ZnBr) and dizinc (BrZn-Ar-ZnBr) compounds. Br Br FG e, Zn anode ZnBr CoCl2 0.2eq FG ZnBr BrZn 2 0.2eq CH3CN-Pyr (v/v= 9/1) RT, I=0.2A FG= H, Me, OMe, F 44–76% Only ortho-dibromobenzenes are little reactive (16% from ortho-dibromobenzene). These dizinc species react with phenyl iodide using palladium as catalyst: BrZn F ZnBr + I PdCl 2(PPh 3) 2 2% 60°C F 45% / Br-Ar-Br In the same procedure, dichlorobenzene reagents give a mixture of mono and dizinc compounds at 4 F mol ±1 of Cl 2Ar. The entire starting reagent is consumed only when dichlorobenzene is activated with an electron-withdrawing group (Eq. (21)) (with dichlorobenzene, 51% of the starting product is recovered at 4 F mol ±1 ). Cl CF 3 Cl e, Zn anode CoCl 2 0.2eq ZnBr 2 0.2eq CH 3CN-Pyr (v/v= 9/1) RT, I=0.2A ClZn 2,5-Dibromothiophenes and 2,5-dichlorothiophenes behave like the corresponding benzene reagents: CF 3 Cl + ClZn 19% 73% CF 3 ZnCl (21) (19) (20) FG 647 35-69% N
648 15 Polyfunctional Zinc, Cobalt and Iron Organometallics Prepared by Electrosynthesis Br S Br e, Zn anode CoCl 2 0.2eq BrZn ZnBr 2 0.2eq CH 3CN-Pyr (v/v= 9/1) RT, I=0.2A S 28% ZnBr The synthesis of alternating p-conjugated copolymers based on this electrochemical preparation of the above mentioned aryldizinc intermediates was obtained by their subsequent cross-coupling with unsaturated dihalogenated compounds using a palladium catalysis [39]: BrZn ZnBr FG + Br-R-Br FG = H, Me, F Br-R-Br = Br S PdCl 2(PPh 3) 2 2% 60°C R FG NO2 Br S Br Br , MeOC , Br , Experimental procedure: Preparation of unsubstituted poly(p-phenylenevinylene) Step 1 is carried out in an undivided cell fitted with a sacrificial zinc anode and stainless steel cathode. The electrolysis is carried out at a constant current of 0.25 A at room temperature until total consumption of the original 1,4-dibromobenzene. For all electrolysis, 1,4-dibromophenylenes are consumed according to the expected faradaic slope, that is 4 F mol ±1 of substrate in a typical experiment, 50 mL of mixture of solvent (45 mL acetonitrile and 5 ml of pyridine) containing 10 mmol of ArX 2 (0.2 M), 2 mmol of CoCl 2 (0.04 M) and 2 mmol (0.2 M) of ZnBr 2 were introduced in the cell. The yields of organozinc compounds thus obtained were estimated as follows: samples of the electrolysis solutions were iodinated, then hydrolyzed with sodium thiosulfate and extracted with diethyl ether. Amounts of iodinated compounds were compared to the amounts of starting aryl bromides via an internal standard by gas chromatography. Step 2 is achieved in the same cell, immediately after electrolysis. An equimolar amount (10 mmol) of 1,2-dihaloethylene is added to the solution, together with 2 mol% of PdCl 2(PPh 3) 2. The solution was stirred and heated at 60 C for 12 h. After this time, both the arylzinc species and 1,2-dihaloethylene are consumed, which was verified by GC. The reaction mixture was poured into a solution of 6N HCl (50 mL) and extracted with diethyl ether (2”25 mL). The combinated extracts were filtered and washed with distilled water, methanol and pentane. 15.4.3.2 In CH 3CN as Solvent Conversion of functionalized aryl bromides (or iodides) in an electrochemical cell fitted with a sacrificial anode, in the presence of cobalt bromide without ligand in acetonitrile affords the corresponding organozinc species in good yields according to Eq. (24) [40]. n Br Br (22) (23)
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Organometallics. Paul Knochel Copyr
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Handbook of Functionalized Organome
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Contents Preface XV List of Authors
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Contents 3.3.9 Oxidation of Functio
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6.3.1 Nucleophilic Addition onto Ca
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9.2.3 Preparation of Functionalized
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13.6.4 Nickel-Catalyzed Cross-coupl
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Preface Since the pioneering work o
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XVIII List of Authors Corinne Gosmi
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1 Introduction Paul Knochel and Fel
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umorganic is directly generated in
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Et H 21 Et AlBu 2 + CO 2Et Cu(CN)Mg
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8 2 Polyfunctional Lithium Organome
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10 2 Polyfunctional Lithium Organom
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R R 12 2 Polyfunctional Lithium Org
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MeO MeO R 14 2 Polyfunctional Lithi
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N 16 2 Polyfunctional Lithium Organ
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Li LiO 20 2 Polyfunctional Lithium
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Li 22 2 Polyfunctional Lithium Orga
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26 Ph O Ni-Pr 2 2 Polyfunctional Li
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28 Li 2 Polyfunctional Lithium Orga
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Li 32 203 2 Polyfunctional Lithium
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36 Br 2 Polyfunctional Lithium Orga
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3 Functionalized Organoborane Deriv
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Br SSiMe 2tBu 4 3.2 Preparation and
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B O O 3.2 Preparation and Reaction
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3.2 Preparation and Reaction of Fun
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Ar H Ar = O HB O CF 3 CF 3 3.2 Prep
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X X Cl Cl TfO Cl 3.2 Preparation an
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HO HO Br OH O X N N O N 3.2 Prepara
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MOMO MOMO I CbzN O 3.2 Preparation
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(HO) 3B O NMe 3 N N O Br 3.2 Prepar
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H H O O N H N H O OEt O O OEt O 3.2
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t BuO2C O N H 3.2 Preparation and R
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R H2O R R B(OH) 2 B(OH) 2 3.3 Prepa
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3.3 Preparation and Reactions of Fu
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R 124 BF 3K Br 3.3 Preparation and
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B O O I OR O OR O O O O O OR 3.3 Pr
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S N O B O I O 133 3.4 Preparation a
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3.5 Synthesis and Reactions of Func
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R TrocO S N R 1 O S N 13 12 O 1 160
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22 H. Nakamura, M. Fujiwara, Y. Yam
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102 K. A. Scheidt, A. Tasaka, T. D.
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4 Polyfunctional Magnesium Organome
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crystallize with four-coordinated M
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4.2Methods of Preparation of Grigna
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NC Br Br 4.2Methods of Preparation
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N N Ph I 4.2Methods of Preparation
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Cl MgBr 4.2Methods of Preparation o
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O O O O 4.2Methods of Preparation o
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O Me Me O Pent I 4.2Methods of Prep
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4.3 Further Applications of Functio
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OTIPS I iPrMgCl OTIPS 4.3 Further A
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4.4 Application of Functionalized M
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I O O OBn Pd(t-Bu 3P) 2 (10 mol%) 4
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Me OTf CO2Et + Me 4.4 Application o
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12 a) F. Bickelhaupt in H. G. Riche
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56 G. Varchi, C. Kofink, D. M. Lind
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kin Trans. 1 1992, 1393; b) M. Sato
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31, 805; J. F. Hartwig, Angew. Chem
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5 Polyfunctional Silicon Organometa
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stereocontrol [5]. Similar chiral c
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5.2 Allylic Silanes seven-membered
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SiMe 3 33 Pr OH OSiMe 3 SiMe 3 34 O
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5.2 Allylic Silanes Although alkyl
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R O Si H 60a (R = H) 60b (R = Me) R
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Bpin SiMe 2Ph (CH 2) 2Ph 73 EtCH(OE
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BnO HO SiMe2Ph 2 BnO CHO BnO O BF3
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5.3 Alkenylsilanes When the same st
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HO I O Si Mo cat. : m n I O Si 111
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5.4Alkylsilanes Transition metal-ca
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5.4Alkylsilanes The fluoride-induce
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5.5 Miscellaneous Preparations and
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5.5 Miscellaneous Preparations and
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716. (c)I. E. Markó, J.-M. Planche
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6 Polyfunctional Tin Organometallic
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phine ligand or Pd II (PPh 3) 2Cl 2
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Bu 3 Sn Scheme 6.4 n-Pent + Me I O
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N N N H 2 I Scheme 6.8 N + Me Sn 3
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O O O NaO HO Me P O OH O OH (+)-Fos
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6.2 Metal-Catalyzed Coupling Reacti
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6.2 Metal-Catalyzed Coupling Reacti
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6.3 Nucleophilic Additions a-hydrox
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6.3 Nucleophilic Additions oxy alde
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6.3 Nucleophilic Additions found ap
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6.3 Nucleophilic Additions 6.3.1.5.
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6.3 Nucleophilic Additions ethylami
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N H 91% (ee:84%) Scheme 6.31 N CO 2
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6.4 Radical Reactions of Organotins
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TsN Scheme 6.37 + Bu 3Sn O Ph AIBN
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6.5.2 Tin-to-lithium Exchange 6.5.2
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Ar OR Scheme 6.42 N H SnBu 3 n-BuLi
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References 1 D. Azarian, S. S. Dua,
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Commun., 2002, 2608±2609; W. Su, S
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110 Y. Obora, M. Nakanishi, M. Toku
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178 Y. Yamamoto, H. Yatagai, Y. Nar
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J. Chem. Soc., Chem. Commun., 1995,
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301 D. P. G. Hamon, R. A. Massy-Wes
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371 I. D. Gridnev, O. L. Tok, N. A.
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252 7 Polyfunctional Zinc Organomet
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BnO H Me 37 :1:1mixtureof diastereo
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262 Me 3Si 7 Polyfunctional Zinc Or
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264 F F 7 Polyfunctional Zinc Organ
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Bu S O IZn(CH 2) 4ZnI 94 268 7 Poly
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OAc MeO I EtO 2C 272 CHO S C N 7 Po
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276 O 7 Polyfunctional Zinc Organom
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280 E 7 Polyfunctional Zinc Organom
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282 MeO 2C O I 7 Polyfunctional Zin
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H Ph 284 7 Polyfunctional Zinc Orga
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288 Ph N 214 O 7 Polyfunctional Zin
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294 IZn AcO 7 Polyfunctional Zinc O
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O 310 7 Polyfunctional Zinc Organom
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318 AcO 7 Polyfunctional Zinc Organ
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EtO 2C 320 MeO 7 Polyfunctional Zin
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MeO O 322 n-Hept O O I Me 7 Polyfun
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MeO 462 324 460 Br I 463 7 Polyfunc
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348 8 Polyfunctional 1,1-Organodime
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350 O 8 Polyfunctional 1,1-Organodi
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CH 2(ZnI) 2 4 362 8 Polyfunctional
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9 Polyfunctional Organocopper Reage
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S 5 CuI·LiCl Cu(CN)Li Li naphthale
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Br CO 2Et I CO 2Et CO 2Et Np 2CuLi
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9.2 Preparation of Functionalized O
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Pent I O O Pent I CO 2Et O Br Pent
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Ph Ph N OMe 1) n-BuLi 2) alkynylcop
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9.3 Applications of Functionalized
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PrCu·MgBr 2·SMe 2 Pr Me H Pr H HO
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19 X. Yang, T. Rotter, C. Piazza, P
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n-C 7H 15 398 10 Functional Organon
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400 10 Functional Organonickel Reag
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O 424 10 Functional Organonickel Re
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TIPSO R 1 Cp 2ClZr O H 426 O N 10 F
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O 438 O Br 10 Functional Organonick
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Cl 442 CN 10 Functional Organonicke
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11 Polyfunctional Metal Carbenes fo
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11.2 Chromium-Templated Cycloadditi
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11.2 Chromium-Templated Cycloadditi
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(CO) 5Cr O Ph 15 1) t Bu t BuOMe, 5
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O MeO O O O O MeO O OMe Cr(CO) 5 Me
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11.2.3 Cyclization of Chromium Olig
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(CO)5Cr OR * O S + OMe 11.2 Chromiu
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[2+2+1] R 1 R 1 OH (CO) 5Cr R 2 (CO
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11.3 Reactions of Higher Nuclearity
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Br O X Br O R 2 R 2 O 85: X = Si-tB
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11.3 Reactions of Higher Nuclearity
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11.4 Metathesis Reactions Catalyzed
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R 2 R 1 O R O 3 O 11.4 Metathesis R
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i Pr i Pr i Pr Me Me (R)-160 Ph O O
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11.5 Transmetallation The dimerizat
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11.6 Metal Carbenes in Peptide Chem
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11.7 Stereoselective Syntheses with
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O O O O 100% H 2N O O O O O 311a Cr
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11.8 Sugar Metal Carbenes as Organo
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References zation reactions that al
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35 (a) C.A. Merlic, Y. You, D.M. Mc
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D. R. Cefalo, P. J. Bonitatebus Jr.
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12 Functionalized Organozirconium a
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12.2 Functionalized Organozirconoce
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Ph O (H)ZrCp Ph O 2Cl Ph O O O 92 %
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i-PrO O OBu-t O H N Scheme 12.15 H
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BnO Scheme 12.19 O BnO + 27 28 Cp 2
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R 1 O O O R R1 R 2 Scheme 12.28 R P
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12.3 Functionalized Organotitanium
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t-BuOOC Scheme 12.44 O CH 3 7.5 mol
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H 13C 6 O R Scheme 12.52 SiMe 3 O T
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O O OEt 87 Scheme 12.59 Scheme 12.6
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40 A. M. Sun, X. Huang, Heteroatom
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13 Manganese Organometallics for th
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13.2.2 Preparation of Organomangane
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13.3 1,2-Addition to Aldehydes and
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13.3.2 Manganese-Mediated Barbier-
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HeptMnX + HeptMnX + Scheme 13.17 Cl
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13.4 Preparation of Ketones by Acyl
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Me 3Si Cl ( ) 3 R Li 80% 82% Scheme
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13.5 1,4-Addition of Organomanganes
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BuM BuMgCl BuMnCl BuMgCl BuCu BuCu
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13.6 Transition-Metal-Catalyzed Cro
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13.6 Transition-Metal-Catalyzed Cro
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I Cl Scheme 13.56 MeO MnCl (1.2 equ
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13.7 Manganese-Mediated Cross-coupl
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13 C. Boucley, G. Cahiez, unpublish
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570 14 Polyfunctional Electrophilic
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η5 η6 η4 η7 574 14 Polyfunction
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51 594 CO 2Me + Fe(CO)3 CO2Me 14 Po
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Page 612 and 613: Table 14.1 Examples of synthetic ap
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Page 622 and 623: Target molecule Disconnections Mult
Page 640 and 641: 15 Polyfunctional Zinc, Cobalt and
Page 642 and 643: Trifluoromethylzinc compounds prepa
Page 644 and 645: 15.3 Electrochemical Synthesis and
Page 646 and 647: 15.3.2 Carbon±Carbon Bond Formatio
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Page 650 and 651: 1eq Br FG + R 2eq OAc e, CoX 2 cat
Page 652 and 653: Cl O + O e, FeBr 2(Bpy) n DMF, Fe a
Page 654 and 655: 15.4 Electrosynthesis of Compounds
Page 662 and 663: 15.5 General Conclusion (industrial
Page 664 and 665: 17 Durandetti, M.; Devaud, M.; Peri
Page 666 and 667: I2 Index b-alkoxyalkylidenemalonic,
Page 668 and 669: I4 Index boronic ester 47 4-boronyl
Page 670 and 671: I6 Index cyclohexadiene 415 cyclohe
Page 672 and 673: I8 Index fluoroalkenylstannane 206
Page 674 and 675: I10 Index iron-catalyzed carbolithi
Page 676 and 677: I12 Index nickel-catalyzed carbozin
Page 678 and 679: I14 Index psicosecarbene complexes
Page 680 and 681: I16 Index Suzuki-Miyaura reaction a
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