Handbook of Functionalized Organometallics Applications in S

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OAc MeO I EtO 2C 272 CHO S C N 7 Polyfunctional Zinc Organometallics for Organic Synthesis Since the isopropyl group is also transferred in the reaction with an electrophile at a comparable rate as the second R group, an excess of electrophile has to be added and tedious separations may be required. A more straightforward approach is possible for diarylzincs. In this case, the I/Zn-exchange can be performed under very mild conditions [97]. 2Ar I + i-Pr2Zn Li(acac) (10mol%) NMP/ether Ar2Zn + 2 i-PrI ArI 25ºC i-PrI ArZni-Pr Li(acac) Scheme 7.38 Li(acac) catalyzed synthesis of diarylzincs. Ar Li Zn(acac) i-Pr ArI The intermediate formation of a zincate enhances the nucleophilic reactivity of the substituents attached to the central zinc atom and makes it more prone to undergo an iodine±zinc exchange reaction. Thus, the addition of catalytic amounts of Li(acac) to an aryl iodide and i-Pr 2Zn allows the transfer of the two i-Pr groups with the formation of Ar 2Zn and i-PrI (2 equiv). This method allows the preparation of highly functionalized diarylzinc reagents bearing an aldehyde function like 113 or an isothiocyanate group like 114 (Scheme 7.39). These diarylzinc reagents undergo typical reactions of diorganozincs. Thus, the acylation of 113 with an acid chloride in the presence of Pd(0) provides the polyfunctional ketone 115 in 75% yield, whereas the reaction of the zinc reagent 114 with Me 3SnCl gives the aryltin derivative 116 in 66% yield. I i-Pr 2Zn (0.55 equiv.) Li(acac) (10 mol%) NMP, 0ºC, 2h i-Pr 2Zn (0.55 equiv.) Li(acac) (10 mol%) NMP, rt, 3h OAc MeO Zn 2 CHO 113 Pd(dba) 2 (2.5 mol%) THF, rt, 5h Scheme 7.39 Functionalized diarylzincs bearing an aldehyde or an isothiocyanate functional group. O P(5mol%) 3 COCl (1.5 equiv.) MeO i-PrI OAc O CHO 115: 75% c-Hex S C N S C N Zn 2 Me3SnCl SnMe3 EtO2C NMP, rt, 3h EtO2C 114 116 :66%
7.2Methods of Preparation of Polyfunctional Organozinc Reagents Mixed diorganozincs are synthetically useful intermediates, especially if one of the group attached to zinc is preferably transferred. The trimethylsilylmethyl group is too unreactive toward most electrophiles and plays the role of a dummy ligand. The preferential transfer of the second R-group attached to zinc is therefore possible in many cases. The reaction of 4-chlorobutylzinc iodide with Me 3Si- CH 2Li in THF at ±78 C provides the mixed diorganozinc reagent 117 that readily undergoes a Michael addition with butyl acrylate in THF:NMP mixtures (Scheme 7.40) [98]. Barbier-type reactions are also well suited for the synthesis of diarylzincs although the functional-group tolerance of this method has not been investigated in detail [99,100]. Cl(CH 2) 4ZnI H 3C Me3SiCH2Li THF, -78 ºC Cl(CH2) 4ZnCH2SiMe3 CO2Bu TMSCl THF/NMP Cl 117 rt, 12 h Br Li, ZnBr 2 ether, sonication 25 ºC, 0.5 h H 3C 118 Zn O Ni(acac) 2 cat. Scheme 7.40 Various syntheses and Michael additions of organozincs. 2 O Me 119 :84% The reaction of 4-bromotoluene with lithium in the presence of zinc bromide in ether affords the corresponding zinc reagent 118 that undergoes a smooth 1,4addition to sterically hindered enones and leads to the cyclopentanone 119 in 67% yield [99]. 7.2.3.2 The Boron±Zinc Exchange Various organoboranes react with Et 2Zn or i-Pr 2Zn providing the corresponding diorganozinc. Pioneered by Zakharin and Okhlobystin [101] and Thiele and coworkers [102], the method provides a general entry to a broad range of diorganozincs. The exchange reaction proceeds usually under mild conditions and tolerates a wide range of functional groups. It is applicable to the preparation of allylic and benzylic diorganozincs as well as secondary and primary dialkylzincs [103] and dialkenylzincs [104]. Remarkably, functionalized alkenes bearing a nitro group or a alkylidenemalonate function are readily hydroborated with Et 2BH [105] prepared in situ and converted to diorganozinc reagents such as 120 and 121. After a copper-catalyzed allylation the expected allylated products 122 and 123 are obtained in high yields (Scheme 7.41) [103]. CO 2Bu CH 3 273
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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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Page 252 and 253: Ar OR Scheme 6.42 N H SnBu 3 n-BuLi
Page 254 and 255: References 1 D. Azarian, S. S. Dua,
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Page 258 and 259: 110 Y. Obora, M. Nakanishi, M. Toku
Page 260 and 261: 178 Y. Yamamoto, H. Yatagai, Y. Nar
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Page 264 and 265: 301 D. P. G. Hamon, R. A. Massy-Wes
Page 266 and 267: 371 I. D. Gridnev, O. L. Tok, N. A.
Page 268 and 269: 252 7 Polyfunctional Zinc Organomet
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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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326 7 Polyfunctional Zinc Organomet
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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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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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