Handbook of Functionalized Organometallics Applications in S

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S 5 CuI·LiCl Cu(CN)Li Li naphthalenide -78 ºC, THF Li naphthalenide -78 ºC, THF EtO 2C Cu* Cu* 1) 2) Br CO 2Et -100 to -78 ºC, 5 - 15 min 7: 80% O O Cl ,TMSCl Scheme 9.3 Michael addition with functionalized organocopper reagents. O Cu CO 2Et ,TMSCl O 6 8: 92% CuI´LiCl with lithium naphthalenide, it is possible to prepare allylic copper species that undergo smooth addition to enones leading to the 1,4-addition product such as 8 in 92% yield [11]. Remote ester-functionalized aryl- and alkyl-copper compounds can be readily prepared by this method [12]. Remarkably stable orthohalophenylcopper reagents obtained by the direct insertion of activated copper undergo substitution reactions with alkyl iodides, benzylic bromides and various acid chlorides [13,14]. CF 2X 2 (X = Br or Cl) CF 3CH 2CH CH 2 70 % Zn (or Cd) DMF, rt DMF, rt Cl F 3C F F3C F Ph I Ph CF3 70 % DMF, rt Scheme 9.4 Preparation and reactions of CF3Cu. 9.2 Preparation of Functionalized Organocopper Reagents CF 3MX + (CF 3) 2M CuX CF 3Cu O 2N DMF, HMPA, 70 ºC DMF, rt Perfluoroalkylcopper reagents have received more attention than perhaps any other perfluorinated organometallic compounds. They can be prepared from perfluoroalkyl iodides and copper metal in polar solvents (such as DMSO, DMS, 9 OTs I O 2N 381 75 % CF 3 H C C CH2 F3C 68 %
382 9 Polyfunctional Organocopper Reagents for Organic Synthesis DMF, HMPA, pyridine) at elevated temperatures (>100 C), by decomposition of perfluoralkyl carboxylates in the presence of copper(i) salts and by transmetallation techniques involving mercury, cadmium, or zinc reagents. The formation of CF 3Cu 9 from CF 2XY (X, Y= Br, Cl) and zinc or cadmium metal in the presence of Cu(i) salts involves the intermediacy of difluorocarbene, which upon reaction with fluoride ion produces CF 3 and hence a mixture of CF 3MX and (CF 3) 2M (M= Zn, Cd). Transmetallation of the cadmium reagent occur at ±30 C, while the zinc species slowly transmetallates to copper at rt. This approach to CF 3Cu provides a convenient reagent for the introduction of the CF 3-substituent into important pharmaceutical and agricultural chemicals. Addition of an equivalent volume of HMPA to the CF 3Cu/DMF solution inhibits the formation of pentafluoroethylcopper and allows the use of this reagent for the trifluoromethylation of aryl iodides even at elevated temperatures. Trifluoromethylation reactions occurring readily at rt or belowdo not require the use of HMPA to stabilize the trifluoromethylcopper solution. Thus, the copper reagent can be readily allylated at rt. The trifluoromethyl-substituted allene is readily formed from propargyl tosylate. Furthermore, CF 3Cu reacts with alkenyl iodides to give the corresponding alkenyl trifluoromethyl compounds (Scheme 9.4) [15]. 9.2.2 Preparation by a Halogen±Copper Exchange Reaction Corey and Posner have shown that the reaction of lithium dialkylcuprates with aryl iodides leads to an iodine±copper exchange as well as to a competitive crosscoupling reaction [16]. Kondo and coworkers have found that by using Me 2CuLi, it was possible to perform an iodine±copper exchange with various functionalized aryl iodides. An excess of Me 2CuLi (2 equiv.) had to be used to quench methyl iodide that was formed during the I/Cu-exchange reaction [17]. It was reported that sterically hindered lithium cuprates like lithium dineopentylcuprate (Np 2CuLi; 10) and Neophyl 2CuLi ((PhMe 2CCH 2) 2CuLi; 11) rapidly react with various functionalized aryl iodides. Thus, the iodoester 12 is converted to the corresponding copper derivative 13 within 15 min at ±30 C. Its reaction with cyclohexenone provides the desired 1,4-addition product 14 in 70% yield (Scheme 9.5) [18]. Interestingly, electron-poor systems also undergo a Br/Cu-exchange. Thus, aryl bromide 15 is readily converted by Neophyl 2CuLi to the cuprate 16 that affords the allylated product 17 in 76% yield (Scheme 9.5). The use of the sterically very hindered Neophyl 2CuLi (11) allows the preparation of arylcopper derivatives bearing a ketone function such as the copper reagent 18. Its reaction with typical electrophiles [1] provides the expected products 19a±d in 68±78% yield (Scheme 9.6) [18]. The I/Cu-exchange is sensitive to the presence of electron-withdrawing groups in close proximity. They accelerate the exchange reaction and play the role of a directing group. Thus, the triiodobenzoate 20 undergoes a selective monoexchange providing the copper-derivative 21 that is readily acylated with CH 3COBr giving the ketone 22 in 65% yield. A second exchange can then be realized with (Neophyl) 2CuLi (11) leading after acylation with a second acyl chloride to the cor-
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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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Page 394 and 395: 9 Polyfunctional Organocopper Reage
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432 10 Functional Organonickel Reag
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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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Table 14.1 Examples of synthetic ap
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602 Entry Target molecule Disconnec
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Entry Target molecule Disconnection
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Target molecule Disconnections Mult
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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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