Handbook of Functionalized Organometallics Applications in S

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13.6 Transition-Metal-Catalyzed Cross-coupling Reactions 13.6.1 Copper-Catalyzed Cross-coupling Reactions 13.6 Transition-Metal-Catalyzed Cross-coupling Reactions Butylmanganese halides prepared in THF easily react with alkyl iodides or bromides at room temperature in the presence of both copper salts (3 to 5% CuCl) and NMP (4to 9 equivalents). The alkylated products are generally obtained in excellent yields (Scheme 13.44) [38]. This procedure is as simple to carry out as the classical Cu-catalyzed Grignard reaction but the yields are generally better and the chemoselectivity is clearly superior. Indeed, numerous functional groups are tolerated such as alkyl halides, tosylates, nitriles, esters and even ketones. BuMnCl + BuMnCl + BuMnCl + Scheme 13.44 Br Cl ( ) 3 Br OTs ( ) 3 Br O ( ) 2 OEt 3% CuCl 2.2LiCl THF-NMP, r.t. 3% CuCl 2.2LiCl THF-NMP, r.t. 3% CuCl 2.2LiCl THF-NMP, r.t. Bu Cl ( ) 3 94% Bu OTs ( ) 3 74% O Bu ( ) 2 OEt In the case of x-halogenoalkylketones the chemoselectivity of the coupling reaction is very impressive. Indeed, in the absence of copper salts, only the 1,2addition product is obtained in excellent yields (Scheme 13.45), whereas in the presence of copper salts the cross-coupling product is formed in high yields and no trace of alcohol is detected (Scheme 13.46). I Scheme 13.45 Br Scheme 13.46 O O MeMnBr Et 2O, r.t. BuMnCl 3% CuCl 2.2LiCl THF-NMP, r.t. I Bu 78% HO 94% O 90% 559
560 13 Manganese Organometallics for the Chemoselective Synthesis of Polyfunctional Compounds The competition between alkylation and conjugate addition reaction has also been studied. Both reactions take place in the presence of copper salts but it is possible to choose the course of the reaction by adding, or not, NMP as cosolvent (Scheme 13.47). C9H19Br + O BuMnCl 3% CuCl O + C9H19Br THF 0ºC Bu 95% 98% C 9H 19Br + Scheme 13.47 O BuMnCl 3% CuCl 2.2LiCl THF-NMP, r.t. C 13H 28 + 93% 98% Thus, x-bromo enones can be selectively alkylated (Scheme 13.48). OctMnCl + Scheme 13.48 O Br ( ) 5 13.6.2 Iron-Catalyzed Cross-coupling Reactions 3% CuCl 4Li 2 THF-NMP, r.t. O O Oct ( ) 5 Fe-catalyzed alkenylation of organomanganese reagents is easily performed at room temperature [39]. The coupling product is obtained in high yields and the stereoselectivity is excellent since no trace of isomerization is detected (Scheme 13.49). OctMnCl + OctMnCl + Scheme 13.49 Bu I Bu I 3% Fe(acac) 3 THF- NMP, r.t. 3% Fe(acac) 3 THF- NMP, r.t. Bu Oct 90% (cis>99%) Bu Oct 84% (trans>98%) 66%
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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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Page 524 and 525: i-PrO O OBu-t O H N Scheme 12.15 H
Page 526 and 527: BnO Scheme 12.19 O BnO + 27 28 Cp 2
Page 530 and 531: R 1 O O O R R1 R 2 Scheme 12.28 R P
Page 534 and 535: 12.3 Functionalized Organotitanium
Page 538 and 539: t-BuOOC Scheme 12.44 O CH 3 7.5 mol
Page 542 and 543: H 13C 6 O R Scheme 12.52 SiMe 3 O T
Page 546 and 547: O O OEt 87 Scheme 12.59 Scheme 12.6
Page 552 and 553: 40 A. M. Sun, X. Huang, Heteroatom
Page 554 and 555: 13 Manganese Organometallics for th
Page 556 and 557: 13.2.2 Preparation of Organomangane
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Page 562 and 563: HeptMnX + HeptMnX + Scheme 13.17 Cl
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Page 566 and 567: Me 3Si Cl ( ) 3 R Li 80% 82% Scheme
Page 568 and 569: 13.5 1,4-Addition of Organomanganes
Page 570 and 571: BuM BuMgCl BuMnCl BuMgCl BuCu BuCu
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Page 576 and 577: I Cl Scheme 13.56 MeO MnCl (1.2 equ
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Page 582 and 583: 570 14 Polyfunctional Electrophilic
Page 586 and 587: η5 η6 η4 η7 574 14 Polyfunction
Page 606 and 607: 51 594 CO 2Me + Fe(CO)3 CO2Me 14 Po
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Target molecule Disconnections Mult
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612 14 Polyfunctional Electrophilic
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15 Polyfunctional Zinc, Cobalt and
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Trifluoromethylzinc compounds prepa
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15.3 Electrochemical Synthesis and
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15.3.2 Carbon±Carbon Bond Formatio
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Cl Cl NC + MeO2C 1eq 2eq e, CoX 2 c
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1eq Br FG + R 2eq OAc e, CoX 2 cat
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Cl O + O e, FeBr 2(Bpy) n DMF, Fe a
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15.4 Electrosynthesis of Compounds
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FG CuCN/LiCl ZnBr 0ºC CuZnBrCN 15.
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15.5 General Conclusion (industrial
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17 Durandetti, M.; Devaud, M.; Peri
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I2 Index b-alkoxyalkylidenemalonic,
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I4 Index boronic ester 47 4-boronyl
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I6 Index cyclohexadiene 415 cyclohe
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I8 Index fluoroalkenylstannane 206
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I10 Index iron-catalyzed carbolithi
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I12 Index nickel-catalyzed carbozin
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I14 Index psicosecarbene complexes
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I16 Index Suzuki-Miyaura reaction a
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