Handbook of Functionalized Organometallics Applications in S

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371 I. D. Gridnev, O. L. Tok, N. A. Gridneva, Y. N. Bubnov, P. R. Schreiner, J. Am. Chem. Soc., 1998, 120, 1034±1043 372 H. Sashida, A. Kuroda, J. Chem. Soc., Perkin Trans. 1, 2000, 1965±1969 373 R. I. Yousef, T. Rüffer, H. Schmidt, D. Steinborn, J. Organomet. Chem., 2002, 655, 111±114 374 J. D. Hoefelmeyer, M. Schulte, F. P. Gabaï, Inorg. Chem., 2001, 40, 3833±3834 375 A. J. Ashe, III, X. Fang, J. W. Kampf, Organometallics, 2001, 20, 2109±2113 References 249
7 Polyfunctional Zinc Organometallics for Organic Synthesis Paul Knochel, Helena Leuser, Liu-Zhu Gong, Sylvie Perrone, and Florian F. Kneisel 7.1 Introduction Organozincs have been known since the preparation of diethylzinc by Frankland in 1849 in Marburg (Germany) [1]. These organometallic reagents were fairly often used to formnew carbon±carbon bonds until Grignard [2] discovered in 1900 a convenient preparation of organomagnesium compounds. These reagents were found to be more reactive species toward a broad range of electrophiles and afforded generally higher yields compared to organozincs. However, some reactions were still performed with zinc organometallics such as the Reformatsky reaction [3] or the Simmons±Smith cyclopropanation [4]. The intermediate organometallics (zinc enolate and zinc carbenoid) were more easy to handle and more selective than the corresponding magnesium organometallics. Remarkably, Hunsdiecker reported in a German patent of 1943 that organozinc reagents bearing long carbon chains terminated by an ester function can be prepared [5]. This functional-group tolerance remained largely ignored by synthetic chemists and it became clear only recently that organozinc compounds are prone to undergo a large range of transmetallations due to the presence of empty low-lying p-orbitals that readily interact with the d-orbitals of many transition metal salts leading to highly reactive intermediates [6]. One can wonder why unreactive zinc reagents can produce highly reactive organometallic intermediates reacting with many electrophiles that are unreactive toward organozincs. This can be explained by the presence of d-orbitals at the transition-metal center that makes a number of new reaction pathways available that were not accessible to the zinc precursors since the empty d-orbitals of zinc are too high in energy to participate to most organic reactions. It is the combination of the high tolerance of functionalities of organozinc derivatives with a facile transmetallation to many transition metal complexes, which makes organozincs such valuable reagents. Especially important are the transmetallation of RZnX reagents to organocopper compounds [6] and to palladium intermediates [7] which allow the performance of cross-coupling reactions with high efficiency (Negishi reaction [7]; Scheme 7.1). Organometallics. Paul Knochel Copyright 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-31131-9 251
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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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Page 218 and 219: 716. (c)I. E. Markó, J.-M. Planche
Page 220 and 221: 6 Polyfunctional Tin Organometallic
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Page 224 and 225: Bu 3 Sn Scheme 6.4 n-Pent + Me I O
Page 226 and 227: N N N H 2 I Scheme 6.8 N + Me Sn 3
Page 228 and 229: O O O NaO HO Me P O OH O OH (+)-Fos
Page 230 and 231: 6.2 Metal-Catalyzed Coupling Reacti
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Page 240 and 241: 6.3 Nucleophilic Additions 6.3.1.5.
Page 242 and 243: 6.3 Nucleophilic Additions ethylami
Page 244 and 245: N H 91% (ee:84%) Scheme 6.31 N CO 2
Page 246 and 247: 6.4 Radical Reactions of Organotins
Page 248 and 249: TsN Scheme 6.37 + Bu 3Sn O Ph AIBN
Page 250 and 251: 6.5.2 Tin-to-lithium Exchange 6.5.2
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,
Page 256 and 257: Commun., 2002, 2608±2609; W. Su, S
Page 258 and 259: 110 Y. Obora, M. Nakanishi, M. Toku
Page 260 and 261: 178 Y. Yamamoto, H. Yatagai, Y. Nar
Page 262 and 263: J. Chem. Soc., Chem. Commun., 1995,
Page 264 and 265: 301 D. P. G. Hamon, R. A. Massy-Wes
Page 268 and 269: 252 7 Polyfunctional Zinc Organomet
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Page 278 and 279: 262 Me 3Si 7 Polyfunctional Zinc Or
Page 280 and 281: 264 F F 7 Polyfunctional Zinc Organ
Page 284 and 285: Bu S O IZn(CH 2) 4ZnI 94 268 7 Poly
Page 288 and 289: OAc MeO I EtO 2C 272 CHO S C N 7 Po
Page 292 and 293: 276 O 7 Polyfunctional Zinc Organom
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Page 298 and 299: 282 MeO 2C O I 7 Polyfunctional Zin
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300 7 Polyfunctional Zinc Organomet
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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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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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