Handbook of Functionalized Organometallics Applications in S

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280 E 7 Polyfunctional Zinc Organometallics for Organic Synthesis O Li ZnCl 2 163a :E=CO 2Et 163b :E=CN t-Bu t-Bu -78 ºC tort,3h O ZnCl OH Ph E PhCHO E 165a :E=CO 2Et; 60 % 165b : E = CN; 56 % Scheme 7.50 Preparation of allylic zinc reagents by fragmentation reaction. ZnCl E 164a :E=CO2Et 164b :E=CN BuLi providing a lithiumalcoholate that, after the addition of ZnCl 2 and an aldehyde, provides the expected addition product 167 with an excellent diastereoselectivity [120]. Oppolzer et al. have shown that the magnesium-ene reaction is a versatile method for adding allylic magnesium reagents to alkenes in an intramolecular fashion [122]. A zinc-ene [123] reaction can be initiated by the addition of BuLi to tert-butyl ketone 168 followed by the addition of zinc chloride. The resulting zincated spiro-derivative 169 is quenched with an acid chloride leading to the ketone 170 in 60% and > 98% syn-diastereoselectivity (Scheme 7.51) [120d]. O O 166 168 1) n-BuLi, THF 0 ºC, 5 min 2) C6H11CHO, ZnCl2 -78 ºC tort,2h 1) n-BuLi, THF 0 ºC, 5 min 2) ZnCl2 -78 ºC tort,3h 169 ZnCl C 6H 11 OH 167 :76%;syn : anti
7.2.5 Preparation of Lithium Triorganozincates 7.2Methods of Preparation of Polyfunctional Organozinc Reagents Lithiumtriorganozincates are best prepared by the reaction of an alkyllithium (3 equiv) with zinc chloride or by the addition of an alkyllithiumto a dialkylzinc in an etheral solvent [124]. Lithium and magnesium trialkylzincates are more reactive compared to dialkylzincs or alkylzinc halides due to the excess of negative charge at the metallic zinc center that confers a higher nucleophilicity to the organic substituents. Thus, lithiumtrialkylzincates readily undergo 1,4-addition reactions to enones [125]. A methyl group can serve as a dummy ligand allowing a somewhat selective transfer of the alkyl substituent (Scheme 7.52) [124]. In the presence of chiral nitrogen-chelating ligands, asymmetric 1,4-addition reactions can be performed with moderate enantioselectivity [126]. Interestingly, the addition of Bu 3ZnLi to nitrostyrene in a chiral solvent mixture of pentane and (S,S)- 1,4-dimethylamino-2,3-dimethoxybutane leads to an optically enriched nitroalkane [127]. Triorganozincates can also be obtained by the reaction of the sulfonate 171 with Me 3ZnLi leading to the cyclopropylidene-alkylzinc reagent 172. Its reaction with an aldehyde provides the allylic alcohol 173 in 57% yield (Scheme 7.52) [124d]. 171 OSO 2 O F BuMeZnLi THF, -78 ºC Me 3ZnLi (2 equiv.) THF, 0 ºC, 2.5 h O 172 Me Me ZnMe 2Li Scheme 7.52 Preparation and reactions of lithium triorganozincates. O Bu 3:97 (95%yield) Ph(CH 2) 2CHO Lithiumtriorganozincates can also be prepared via an I/Zn-exchange reaction. The exchange is highly chemoselective and tolerates sensitive functional groups like an epoxide or an ester. The reaction of aryl iodides 174a,b with Me 3ZnLi provides the functionalized lithiumzincates 175a,b that undergo respectively a ring closure and an addition to PhCHO leading to the products 176a,b in satisfactory yields (Scheme 7.53) [128]. Immobilized zincates such as 177 can be prepared by treating serine-bound 4iodobenzoate with t-Bu 3ZnLi at 0 C. They react readily with aldehydes. Transmetallation with lithium(2-thienyl)cyanocuprate provides the copper species 178 that undergoes 1,4-additions. Lithiumtrialkylzincates can be used for the preparation of benzylic zinc reagents using a very elegant approach of Harada. Thus, the treat- Ph 281 Me OH 173 :57%
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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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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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Page 310 and 311: 294 IZn AcO 7 Polyfunctional Zinc O
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330 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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