Handbook of Functionalized Organometallics Applications in S

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11.7 Stereoselective Syntheses with Sugar Metal Carbenes The modification of the anomeric center of cyclic carbohydrates into a metalcoordinated carbene carbon leads to glycosylidene complexes. This type of sugar metal carbenes requires different synthetic strategies that may be based on either stochiometric olefin metathesis (see also Section 11.4) of 1-enitols with a strongly electrophilic metal carbene or on a glycal metallation/electrophilic addition sequence. Furanosylidene complexes were synthesized by olefin metathesis of hept-1-enitol 309 with diphenylcarbene complexes 310. Whereas the chromium furanosylidene 311a is obtained in synthetically useful yield, only marginal amounts of the tungsten analog can be isolated under various conditions (Scheme 11.63) [118]. This result may reflect the oxophilicity of tungsten and side reactions arising therefrom. O O 309 O O O + (CO) 5M CPh2 M=Cr; RT, 90 min M=W; 90ºC, 90 min n-heptane a M = Cr b M = W O O O O O 311a: 65% 311b: 3% + H 2C CPh 2 M(CO)5 310a,b Scheme 11.63 Synthesis of metal furanosylidenes based on stoichiometric olefin metathesis. The olefin metathesis approach cannot be extended as an attractive route to metal pyranosylidenes. Instead, an alternative strategy has been developed starting from lithioglycals that are generated in situ by transmetallation of stannylated precursors. As shown for the glucose series, lithiation of stannyl glucals 312 followed by addition of hexacarbonyl chromium gives the acyl chromates which upon alkylation afford the a,b-unsaturated chromium glucal carbenes 317 (route D) according to the Fischer route. Modification of the chromium electrophile by substitution of one carbonyl ligand for a more labile ligand such as THF, however, favors the addition of the lithioglucal to the metal center generating the chromium enolates 314 (route A). At temperatures above 0 C, these intermediates undergo a Ferrier-type rearrangement under elimination of the protected hydroxy group at C-3 to give the a,b-unsaturated chromium glycosylidenes 316 (route C). At low temperature, the elimination can be avoided and the chromium enolates can be trapped with electrophiles to afford the desired 2-deoxy-glycosylidene complexes 315 (route B). Depending on the nature of the electrophile used deuterated or C-2 linked C-glycosidic complexes are also accessible. The stereochemical outcome of the addition of the electrophile can be controlled by the pattern of the protective groups; diastereoselectivities range from 4 to ³90% d.e. (Scheme 11.64) [119]. 491
492 11 Polyfunctional Metal Carbenes for Organic Synthesis RO RO RO RO O SnBu3 RO A RO OR´ 312a,b D O OR´ 317a,b Cr(CO) 5 OMe RO RO A: 1) THF, n BuLi, -78ºC 2) [(CO)5CrTHF], -78ºC -> 0ºC B: THF, EX, -78ºC -> 0ºC a R-R = CMe2, R´ = triisopropylsilyl (TIPS) b R = R´ = TIPS O Cr(CO) 5 OR´ 314a,b O Li OR´ 313a,b RO B RO RO C: T>0ºC EX 2-R/S Yield [%] 315a I only S detectable 59 CF3COOD 58 : 42 50 HCl - 71 315b I 6 : 94 74 CF3COOD
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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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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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Page 472 and 473: O MeO O O O O MeO O OMe Cr(CO) 5 Me
Page 474 and 475: 11.2.3 Cyclization of Chromium Olig
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Page 478 and 479: [2+2+1] R 1 R 1 OH (CO) 5Cr R 2 (CO
Page 480 and 481: 11.3 Reactions of Higher Nuclearity
Page 482 and 483: Br O X Br O R 2 R 2 O 85: X = Si-tB
Page 484 and 485: 11.3 Reactions of Higher Nuclearity
Page 486 and 487: 11.4 Metathesis Reactions Catalyzed
Page 488 and 489: R 2 R 1 O R O 3 O 11.4 Metathesis R
Page 490 and 491: i Pr i Pr i Pr Me Me (R)-160 Ph O O
Page 492 and 493: 11.5 Transmetallation The dimerizat
Page 494 and 495: 11.6 Metal Carbenes in Peptide Chem
Page 496 and 497: 11.7 Stereoselective Syntheses with
Page 506 and 507: O O O O 100% H 2N O O O O O 311a Cr
Page 508 and 509: 11.8 Sugar Metal Carbenes as Organo
Page 510 and 511: References zation reactions that al
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Page 514 and 515: D. R. Cefalo, P. J. Bonitatebus Jr.
Page 516 and 517: 12 Functionalized Organozirconium a
Page 518 and 519: 12.2 Functionalized Organozirconoce
Page 520 and 521: Ph O (H)ZrCp Ph O 2Cl Ph O O O 92 %
Page 524 and 525: i-PrO O OBu-t O H N Scheme 12.15 H
Page 526 and 527: BnO Scheme 12.19 O BnO + 27 28 Cp 2
Page 530 and 531: R 1 O O O R R1 R 2 Scheme 12.28 R P
Page 534 and 535: 12.3 Functionalized Organotitanium
Page 538 and 539: t-BuOOC Scheme 12.44 O CH 3 7.5 mol
Page 542 and 543: H 13C 6 O R Scheme 12.52 SiMe 3 O T
Page 546 and 547: O O OEt 87 Scheme 12.59 Scheme 12.6
Page 552 and 553: 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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