Handbook of Functionalized Organometallics Applications in S

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4.2Methods of Preparation of Grignard Reagents and their Uncatalyzed Reactions tems proved to undergo a fast exchange reaction leading to Grignard reagent 261, no enantioselective I/Mg-exchange reaction could be observed for the enantiotopic iodides of 260 by using chiral ligands on the exchange reagent, such as 262 (Scheme 4.55). Thus, alcohol 263 is obtained in good yield, but the enantiomeric excess is only moderate (83%, 53%ee). Ph I I iPrMgL * Ph MgL * THF, -78 ºC 2h I PhCHO Me2AlCl Ph I Ph OH 260 261 263: 83%, d.s. 93% 53% ee Tol EtMgCl S O Ph Cl 264 (97% ee) THF, -78 ºC 2h ClMg Cl 265 PhCHO Ph Me2AlCl -78 ºC tort O Ph Ph 266: 70%, 93% ee Scheme 4.55 Synthesis of chiral Grignard reagents. A solution to this problem was found by using the sulfoxide±magnesium exchange. Starting with the chiral sulfoxide 264, the reaction with EtMgCl leads to Grignard reagent 265, which reacts with benzaldehyde and leads after cyclization to epoxide 266 in 70% yield, without almost any loss of enantiomeric excess (93% ee) (Scheme 4.55). A very interesting application of carbenoid chemistry is found in the synthesis of substituted pyrimidines 267, developed by Oshima. Using a geminal dibromo-oxime ether 268 and nBuMgBr as exchange reagent, magnesium carbenoid 269 is easily accessible and provides an interesting way to pyrimidines (Scheme 4.56). MeO N Br Ph Br 268 nBuMgBr nBuMgBr (2.2 equiv) THF, -40 ºC tort MeO N nBuMgBr MeO N Ph MgBr Ph MgBr Br Bu 269 270 Scheme 4.56 Pyrimidine synthesis using magnesium carbenoids. N N Ph Ph 267: 74% Ph nBu N 271 269 Bu L * = N HN 145 262 O O SAr
Bu Bn O 146 N O N Bn NMe 2 4 Polyfunctional Magnesium Organometallics for Organic Synthesis Thus, the reaction with another equivalent of nBuMgCl provides substituted Grignard 270 that cyclizes to aziridine 271. Further reaction with another molecule of carbenoid 269, followed by a rearrangement and elimination of methanol leads to pyrimidine 267 in 74% yield (Scheme 4.56). 4.3 Further Applications of Functionalized Grignard Reagents Along with the standard 1,2-addition reactions to carbonyl groups or copper-catalyzed substitution reactions that were shown in the previous sections, functionalized Grignard reagents have found several other applications in synthesis. Thus, the addition to imminium salts, for example, is a very potent method for the preparation of benzylic amines. The Grignard reagent 272 adds to the imminium trifluoroacetate 273 at ±40 C within 30 min in a THF/CH 2Cl 2 mixture providing the bis-allylamine 274 in 76% yield [135]. Similarly, heterocyclic Grignard reagents undergo this aminomethylation. For instance, magnesiated uracil 275 reacts within 1 h with iminium salt 273 and leads to compound 276 in 85% yield (Scheme 4.57) [98,136]. 276: 85% N(allyl) 2 O Bn N MgBr O N Bn THF, 1 h -40 ºC tort 277 275 NMe 2 Bu OTf N CH 2 OCOCF 3 273 MgBr MgBr CO 2Et NMe 2 CO2Et THF/NMP -78 ºC, 30 min CO2Et THF/NMP -65 ºC, 30 min Ph CO2Et 280: 80% 279 281: 80% Scheme 4.57 Reaction of functionalized arylmagnesium compounds with imminium salts. Ph 278 272 THF/CH 2Cl 2, -40 ºC, 30 min OTf 274: 76% NMe 2 N(allyl) 2 CO 2Et Various unsaturated iminium salts like 277 and 278 react with functionalized arylmagnesium halides, such as 279 furnishing the expected benzylic amines 280 and 281 in 80% yield (Scheme 4.57) [137]. Aryl sulfonamides such as 282 are of considerable medicinal importance [138]. In order to provide a generally useful, mild methodology for the synthesis of sulfonamides, allowing the variation at both nitrogen and sulfur, Barrett and coworkers developed a procedure starting
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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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Page 112 and 113: 3.7 Synthesis and Reactions of Func
Page 116 and 117: R TrocO S N R 1 O S N 13 12 O 1 160
Page 122 and 123: 22 H. Nakamura, M. Fujiwara, Y. Yam
Page 124 and 125: 102 K. A. Scheidt, A. Tasaka, T. D.
Page 126 and 127: 4 Polyfunctional Magnesium Organome
Page 128 and 129: crystallize with four-coordinated M
Page 130 and 131: 4.2Methods of Preparation of Grigna
Page 136 and 137: NC Br Br 4.2Methods of Preparation
Page 138 and 139: N N Ph I 4.2Methods of Preparation
Page 144 and 145: Cl MgBr 4.2Methods of Preparation o
Page 158 and 159: O O O O 4.2Methods of Preparation o
Page 160 and 161: O Me Me O Pent I 4.2Methods of Prep
Page 164 and 165: 4.3 Further Applications of Functio
Page 170 and 171: OTIPS I iPrMgCl OTIPS 4.3 Further A
Page 172 and 173: 4.4 Application of Functionalized M
Page 174 and 175: I O O OBn Pd(t-Bu 3P) 2 (10 mol%) 4
Page 178 and 179: Me OTf CO2Et + Me 4.4 Application o
Page 182 and 183: 12 a) F. Bickelhaupt in H. G. Riche
Page 184 and 185: 56 G. Varchi, C. Kofink, D. M. Lind
Page 186 and 187: kin Trans. 1 1992, 1393; b) M. Sato
Page 188 and 189: 31, 805; J. F. Hartwig, Angew. Chem
Page 190 and 191: 5 Polyfunctional Silicon Organometa
Page 192 and 193: stereocontrol [5]. Similar chiral c
Page 194 and 195: 5.2 Allylic Silanes seven-membered
Page 196 and 197: SiMe 3 33 Pr OH OSiMe 3 SiMe 3 34 O
Page 198 and 199: 5.2 Allylic Silanes Although alkyl
Page 200 and 201: R O Si H 60a (R = H) 60b (R = Me) R
Page 202 and 203: Bpin SiMe 2Ph (CH 2) 2Ph 73 EtCH(OE
Page 204 and 205: BnO HO SiMe2Ph 2 BnO CHO BnO O BF3
Page 206 and 207: 5.3 Alkenylsilanes When the same st
Page 208 and 209: HO I O Si Mo cat. : m n I O Si 111
Page 210 and 211: 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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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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