Handbook of Functionalized Organometallics Applications in S

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BnO H Me 37 :1:1mixtureof diastereomers Me 3Si BuO 260 7 Polyfunctional Zinc Organometallics for Organic Synthesis I I O O ZnX O SiMe3 O HO O OBn Et 2Zn (2 equiv.) PdCl 2(dppf) 1.5 mol% 25 ºC, 5 h BnO Et2Zn Ni(acac) 2 cat. H A H Me O O ZnX BnO 2) PhCOCl XZn 38 1) CuCN·2LiCl Me O Ph O O 40 :62%(>98:2) EtO 2C 1) CuCN·2LiCl 2) CO2Et Br BnO 3 2 Me 1 Scheme 7.16 Pd- and Ni-catalyzed radical cyclization leading to zinc organometallics. CHO OBu CO 2Me Pent 2Zn Ti(OiPr) 4 N(H)Tf N(H)Tf 8mol% 1) H2 Pd/BaSO4 cat. pyridine, 92 % 2) BCl3,CH2Cl2 -78 ºC to-10ºC OHC Pent O c-Hex N C Me I 57 % OH 61 % Me 3Si Pent OBu N c-Hex Et CO 2Me OH 70 %; 92 % ee Jones oxid. acetone OBn I BuO NBS, CH 2Cl 2 HO 2C Pent O O 55 % 90 % CO 2Me Dess-Martin oxid. 81 % 2) CuCN·2LiCl 3) Br Et -55 ºC, 48 h O Pent Me 3Si O 1step 1) Et 2Zn Ni(acac) 2 cat. THF, 25 ºC Et CO 2Me Br OBu HO 2C 42 : cis-methyl jasmonate Pent O O OBn 39 :71% 1) Et2Zn Ni(acac) 2 THF, 40 ºC 2) O2,TMSCl THF, -5 ºC 41 : (-)-methylenolactocin 86 % ; 95 : 5 Scheme 7.17 Preparation of (±)-methylenolactocin (41) and cis-methyl jasmonate (42). Et CO2Me
FG-RCH 2Br + Et 2Zn 43 : FG = ester, nitrile, chloride 7.2Methods of Preparation of Polyfunctional Organozinc Reagents MnBr2 (5 mol%) CuCl (3 mol%) DMPU Scheme 7.18 Mixed Mn/Cu-catalyzed alkylzinc bromides synthesis. FG-RCH 2ZnBr + CH 2=CH 2 + EtH (> 80 %) Interestingly, low-valent cobalt species obtained by the in situ reduction of CoBr 2 with zinc catalyze the reaction of aryl bromides with zinc dust. The reaction allows the preparation of a range of functionalized arylzinc halides such as 44 (Scheme 7.19) [45]. Br O O CoBr2 (0.1 equiv.) ZnBr2 ( 0.1 equiv.) Zn (3 equiv.) CH3CN, rt, 0.5 h ZnBr O O 44 :>80% Scheme 7.19 Cobalt-mediated insertion of zinc to aryl bromides. In summary, the direct insertion of zinc dust to organic halides is an excellent method for preparing a broad range of polyfunctional organozinc halides bearing various functional groups like an ester [46], an ether, an acetate [47], a ketone, cyano [48], halide [49], N,N-bis(trimethylsilyl)amino [50], primary and secondary amino, amide phthalimide [51], sulfide, sulfoxide and sulfone [52], boronic ester [53], enone [54] or a phosphonate [55]. An alternative method is based on transmetallation reactions. 7.2.2.2 Preparation of Organozinc Halides using Transmetallation Reactions A number of transmetallation procedures leading to zinc organometallics can be performed. Many organometallics having a polar C±Met bond are readily transmetallated by the reaction with a zinc salt to the more covalent organozinc compounds. The synthetic scope of these transmetallations depends on the availability of the starting organometallic species and on its compatibility with functional groups. Although organolithiums are highly reactive organometallic species, it is possible to prepare aryllithiumspecies bearing cyano groups [56] or nitro groups [57] at very low temperature (±100 C to ±90 C). By performing a halogen±lithium exchange reaction, followed by a transmetallation with ZnBr 2, functionalized organometallics are prepared that cannot be obtained by the insertion of zinc to the corresponding organic halide. Azides inhibit the direct zinc insertion to an organic halide. However, the reaction of the alkenyl iodide 45 bearing an azide group with n-BuLi at ±100 C followed by the transmetallation with ZnBr 2 in THF at ±90 C provides the expected zinc reagent 46 in > 85% yield (Scheme 7.20) [58]. 261
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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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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
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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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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
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Page 298 and 299: 282 MeO 2C O I 7 Polyfunctional Zin
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O 310 7 Polyfunctional Zinc Organom
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312 7 Polyfunctional Zinc Organomet
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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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