Handbook of Functionalized Organometallics Applications in S

More documents

Recommendations

Info

Preface Since the pioneering work of Frankland and Wurtz, organometallic intermediates have occupied a central position in organic synthesis. The chemical behavior of organometallic reagents depends greatly on the nature of the metal and on the carbon hybridization. Each metal has intrinsic chemical properties, which confer a specific reactivity for forming new carbon-carbon bonds to the organic moiety attached to it. The nature of the metal substituents (ligands) enables a modulation and adjustment to this reactivity of the organometallic to the organic substrate. Choosing the correct metal and ligand sphere to achieve any given transformation represents a major task for the synthetic chemist. During the course of the last thirty years, chemists have realized that this fine-tuning of the reactivity of organometallics has a number of synthetic advantages (selectivity, yields, reaction conditions, etc.). However, they have also noticed that a broad range of functionalities can be present in the organometallic intermediate itself and therefore these reagents allow for the preparation of polyfunctional molecules without the need for multiple protection and deprotection steps. This book summarizes the synthetic knowledge available as of 2005 for preparing functionalized organometallics and the optimum conditions for their reacting with electrophilic species. It also covers main group and transition organometallics while outlining in detail the functional group compatibility for each class of organometallics in the various book chapters. Organometallic chemistry is a field of chemistry that is constantly experiencing discoveries and is one of the motors of chemistry. Thus it can be expected that numerous new synthetic methods based on the use of functionalized organometallics will be added to the chemistry presented in this book within the next few years. An effort has been made to present the material in an attractive layout with many equations and numerous practical details, allowing for rapidly entry in the field. Therefore, this book is well suited for master and PhD students, for advanced undergraduate students, as well as industrial process and research chemists. Munich, August 2005 Paul Knochel Organometallics. Paul Knochel Copyright 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-31131-9 XV
List of Authors Oliver Baron Department of Chemistry Ludwig-Maximilians-Universität Butenandtstrasse 5±13, Haus F 81377 München Germany Gerard Cahiez Departement de Chimie, ESCOM UniversitØ de Paris 13, Boulevard de l'Hautil 95092 Cergy-Pontoise France Helena Chechik-Lankin Department of Chemistry Technion-Israel Institute of Technology Technion City Haifa 32000 Israel Karl-Heinz Dötz KØkulØ-Institut für Organische Chemie und Biochemie Gerhard-Domagk-Strasse 1 53121 Bonn Germany Organometallics. Paul Knochel Copyright 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-31131-9 Francisco Foubelo Departamento de Química Orgµnica Facultad de Ciencias and Instituto de Síntesis Orgµnica (ISO) Universidad de Alicante Apdo. 99 03080 Alicante Spain Eric Fouquet Laboratoire de Chimie Organique et Organometallique UniversitØ de Bordeaux I 351, Cours de la Liberation 33405 Talence Cedex France Nina Gommermann Department of Chemistry Ludwig-Maximilians-Universität Butenandtstrasse 5±13, Haus F 81377 München Germany Liu-Zhu Gong Department of Chemistry Ludwig-Maximilians-Universität Butenandtstrasse 5±13, Haus F 81377 München Germany XVII
Page 2 and 3: Organometallics. Paul Knochel Copyr
Page 4 and 5: Handbook of Functionalized Organome
Page 6 and 7: Contents Preface XV List of Authors
Page 8 and 9: Contents 3.3.9 Oxidation of Functio
Page 10 and 11: 6.3.1 Nucleophilic Addition onto Ca
Page 12 and 13: 9.2.3 Preparation of Functionalized
Page 14 and 15: 13.6.4 Nickel-Catalyzed Cross-coupl
Page 18 and 19: XVIII List of Authors Corinne Gosmi
Page 20 and 21: 1 Introduction Paul Knochel and Fel
Page 22 and 23: umorganic is directly generated in
Page 24 and 25: Et H 21 Et AlBu 2 + CO 2Et Cu(CN)Mg
Page 26 and 27: 8 2 Polyfunctional Lithium Organome
Page 28 and 29: 10 2 Polyfunctional Lithium Organom
Page 30 and 31: R R 12 2 Polyfunctional Lithium Org
Page 32 and 33: MeO MeO R 14 2 Polyfunctional Lithi
Page 34 and 35: N 16 2 Polyfunctional Lithium Organ
Page 38 and 39: Li LiO 20 2 Polyfunctional Lithium
Page 40 and 41: Li 22 2 Polyfunctional Lithium Orga
Page 44 and 45: 26 Ph O Ni-Pr 2 2 Polyfunctional Li
Page 46 and 47: 28 Li 2 Polyfunctional Lithium Orga
Page 50 and 51: Li 32 203 2 Polyfunctional Lithium
Page 54 and 55: 36 Br 2 Polyfunctional Lithium Orga
Page 62 and 63: 3 Functionalized Organoborane Deriv
Page 64 and 65: Br SSiMe 2tBu 4 3.2 Preparation and
Page 66 and 67:
B O O 3.2 Preparation and Reaction
Page 68 and 69:
3.2 Preparation and Reaction of Fun
Page 70 and 71:
Page 72 and 73:
Ar H Ar = O HB O CF 3 CF 3 3.2 Prep
Page 74 and 75:
Page 76 and 77:
X X Cl Cl TfO Cl 3.2 Preparation an
Page 78 and 79:
HO HO Br OH O X N N O N 3.2 Prepara
Page 80 and 81:
MOMO MOMO I CbzN O 3.2 Preparation
Page 82 and 83:
Page 84 and 85:
(HO) 3B O NMe 3 N N O Br 3.2 Prepar
Page 86 and 87:
H H O O N H N H O OEt O O OEt O 3.2
Page 88 and 89:
t BuO2C O N H 3.2 Preparation and R
Page 90 and 91:
Page 92 and 93:
Page 94 and 95:
Page 96 and 97:
R H2O R R B(OH) 2 B(OH) 2 3.3 Prepa
Page 98 and 99:
3.3 Preparation and Reactions of Fu
Page 100 and 101:
R 124 BF 3K Br 3.3 Preparation and
Page 102 and 103:
B O O I OR O OR O O O O O OR 3.3 Pr
Page 104 and 105:
S N O B O I O 133 3.4 Preparation a
Page 106 and 107:
3.5 Synthesis and Reactions of Func
Page 108 and 109:
Page 110 and 111:
Page 112 and 113:
Page 114 and 115:
Page 116 and 117:
R TrocO S N R 1 O S N 13 12 O 1 160
Page 118 and 119:
Page 120 and 121:
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 132 and 133:
Page 134 and 135:
Page 136 and 137:
NC Br Br 4.2Methods of Preparation
Page 138 and 139:
N N Ph I 4.2Methods of Preparation
Page 140 and 141:
Page 142 and 143:
Page 144 and 145:
Cl MgBr 4.2Methods of Preparation o
Page 146 and 147:
Page 148 and 149:
Page 150 and 151:
Page 152 and 153:
Page 154 and 155:
Page 156 and 157:
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 162 and 163:
Page 164 and 165:
4.3 Further Applications of Functio
Page 166 and 167:
Page 168 and 169:
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 176 and 177:
Page 178 and 179:
Me OTf CO2Et + Me 4.4 Application o
Page 180 and 181:
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
Page 212 and 213:
5.4Alkylsilanes The fluoride-induce
Page 214 and 215:
5.5 Miscellaneous Preparations and
Page 216 and 217:
5.5 Miscellaneous Preparations and
Page 218 and 219:
716. (c)I. E. Markó, J.-M. Planche
Page 220 and 221:
6 Polyfunctional Tin Organometallic
Page 222 and 223:
phine ligand or Pd II (PPh 3) 2Cl 2
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
Page 232 and 233:
6.2 Metal-Catalyzed Coupling Reacti
Page 234 and 235:
6.3 Nucleophilic Additions a-hydrox
Page 236 and 237:
6.3 Nucleophilic Additions oxy alde
Page 238 and 239:
6.3 Nucleophilic Additions found ap
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 266 and 267:
371 I. D. Gridnev, O. L. Tok, N. A.
Page 268 and 269:
252 7 Polyfunctional Zinc Organomet
Page 270 and 271:
Page 272 and 273:
Page 274 and 275:
Page 276 and 277:
BnO H Me 37 :1:1mixtureof diastereo
Page 278 and 279:
262 Me 3Si 7 Polyfunctional Zinc Or
Page 280 and 281:
264 F F 7 Polyfunctional Zinc Organ
Page 282 and 283:
Page 284 and 285:
Bu S O IZn(CH 2) 4ZnI 94 268 7 Poly
Page 286 and 287:
Page 288 and 289:
OAc MeO I EtO 2C 272 CHO S C N 7 Po
Page 290 and 291:
Page 292 and 293:
276 O 7 Polyfunctional Zinc Organom
Page 294 and 295:
Page 296 and 297:
280 E 7 Polyfunctional Zinc Organom
Page 298 and 299:
282 MeO 2C O I 7 Polyfunctional Zin
Page 300 and 301:
H Ph 284 7 Polyfunctional Zinc Orga
Page 302 and 303:
Page 304 and 305:
288 Ph N 214 O 7 Polyfunctional Zin
Page 306 and 307:
Page 308 and 309:
Page 310 and 311:
294 IZn AcO 7 Polyfunctional Zinc O
Page 312 and 313:
Page 314 and 315:
Page 316 and 317:
Page 318 and 319:
Page 320 and 321:
Page 322 and 323:
Page 324 and 325:
Page 326 and 327:
O 310 7 Polyfunctional Zinc Organom
Page 328 and 329:
Page 330 and 331:
Page 332 and 333:
Page 334 and 335:
318 AcO 7 Polyfunctional Zinc Organ
Page 336 and 337:
EtO 2C 320 MeO 7 Polyfunctional Zin
Page 338 and 339:
MeO O 322 n-Hept O O I Me 7 Polyfun
Page 340 and 341:
MeO 462 324 460 Br I 463 7 Polyfunc
Page 342 and 343:
Page 344 and 345:
Page 346 and 347:
Page 348 and 349:
Page 350 and 351:
Page 352 and 353:
Page 354 and 355:
Page 356 and 357:
Page 358 and 359:
Page 360 and 361:
Page 362 and 363:
Page 364 and 365:
348 8 Polyfunctional 1,1-Organodime
Page 366 and 367:
350 O 8 Polyfunctional 1,1-Organodi
Page 368 and 369:
Page 370 and 371:
Page 372 and 373:
Page 374 and 375:
Page 376 and 377:
Page 378 and 379:
CH 2(ZnI) 2 4 362 8 Polyfunctional
Page 380 and 381:
Page 382 and 383:
Page 384 and 385:
Page 386 and 387:
Page 388 and 389:
Page 390 and 391:
Page 392 and 393:
Page 394 and 395:
9 Polyfunctional Organocopper Reage
Page 396 and 397:
S 5 CuI·LiCl Cu(CN)Li Li naphthale
Page 398 and 399:
Br CO 2Et I CO 2Et CO 2Et Np 2CuLi
Page 400 and 401:
9.2 Preparation of Functionalized O
Page 402 and 403:
Pent I O O Pent I CO 2Et O Br Pent
Page 404 and 405:
Ph Ph N OMe 1) n-BuLi 2) alkynylcop
Page 406 and 407:
9.3 Applications of Functionalized
Page 408 and 409:
PrCu·MgBr 2·SMe 2 Pr Me H Pr H HO
Page 410 and 411:
19 X. Yang, T. Rotter, C. Piazza, P
Page 412 and 413:
n-C 7H 15 398 10 Functional Organon
Page 414 and 415:
400 10 Functional Organonickel Reag
Page 416 and 417:
Page 418 and 419:
Page 420 and 421:
Page 422 and 423:
Page 424 and 425:
Page 426 and 427:
Page 428 and 429:
Page 430 and 431:
Page 432 and 433:
Page 434 and 435:
Page 436 and 437:
Page 438 and 439:
O 424 10 Functional Organonickel Re
Page 440 and 441:
TIPSO R 1 Cp 2ClZr O H 426 O N 10 F
Page 442 and 443:
Page 444 and 445:
Page 446 and 447:
Page 448 and 449:
Page 450 and 451:
Page 452 and 453:
O 438 O Br 10 Functional Organonick
Page 454 and 455:
Page 456 and 457:
Cl 442 CN 10 Functional Organonicke
Page 458 and 459:
Page 460 and 461:
Page 462 and 463:
Page 464 and 465:
11 Polyfunctional Metal Carbenes fo
Page 466 and 467:
11.2 Chromium-Templated Cycloadditi
Page 468 and 469:
11.2 Chromium-Templated Cycloadditi
Page 470 and 471:
(CO) 5Cr O Ph 15 1) t Bu t BuOMe, 5
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
Page 476 and 477:
(CO)5Cr OR * O S + OMe 11.2 Chromiu
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 498 and 499:
Page 500 and 501:
Page 502 and 503:
Page 504 and 505:
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
Page 512 and 513:
35 (a) C.A. Merlic, Y. You, D.M. Mc
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 522 and 523:
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 528 and 529:
Page 530 and 531:
R 1 O O O R R1 R 2 Scheme 12.28 R P
Page 532 and 533:
Page 534 and 535:
12.3 Functionalized Organotitanium
Page 536 and 537:
Page 538 and 539:
t-BuOOC Scheme 12.44 O CH 3 7.5 mol
Page 540 and 541:
Page 542 and 543:
H 13C 6 O R Scheme 12.52 SiMe 3 O T
Page 544 and 545:
Page 546 and 547:
O O OEt 87 Scheme 12.59 Scheme 12.6
Page 548 and 549:
Page 550 and 551:
Page 552 and 553:
40 A. M. Sun, X. Huang, Heteroatom
Page 554 and 555:
13 Manganese Organometallics for th
Page 556 and 557:
13.2.2 Preparation of Organomangane
Page 558 and 559:
13.3 1,2-Addition to Aldehydes and
Page 560 and 561:
13.3.2 Manganese-Mediated Barbier-
Page 562 and 563:
HeptMnX + HeptMnX + Scheme 13.17 Cl
Page 564 and 565:
13.4 Preparation of Ketones by Acyl
Page 566 and 567:
Me 3Si Cl ( ) 3 R Li 80% 82% Scheme
Page 568 and 569:
13.5 1,4-Addition of Organomanganes
Page 570 and 571:
BuM BuMgCl BuMnCl BuMgCl BuCu BuCu
Page 572 and 573:
13.6 Transition-Metal-Catalyzed Cro
Page 574 and 575:
13.6 Transition-Metal-Catalyzed Cro
Page 576 and 577:
I Cl Scheme 13.56 MeO MnCl (1.2 equ
Page 578 and 579:
13.7 Manganese-Mediated Cross-coupl
Page 580 and 581:
13 C. Boucley, G. Cahiez, unpublish
Page 582 and 583:
570 14 Polyfunctional Electrophilic
Page 584 and 585:
Page 586 and 587:
η5 η6 η4 η7 574 14 Polyfunction
Page 588 and 589:
Page 590 and 591:
Page 592 and 593:
Page 594 and 595:
Page 596 and 597:
Page 598 and 599:
Page 600 and 601:
Page 602 and 603:
Page 604 and 605:
Page 606 and 607:
51 594 CO 2Me + Fe(CO)3 CO2Me 14 Po
Page 608 and 609:
Page 610 and 611:
Page 612 and 613:
Table 14.1 Examples of synthetic ap
Page 614 and 615:
602 Entry Target molecule Disconnec
Page 616 and 617:
Entry Target molecule Disconnection
Page 618 and 619:
Page 620 and 621:
Page 622 and 623:
Target molecule Disconnections Mult
Page 624 and 625:
Page 626 and 627:
Page 628 and 629:
Page 630 and 631:
Page 632 and 633:
Page 634 and 635:
Page 636 and 637:
Page 638 and 639:
Page 640 and 641:
15 Polyfunctional Zinc, Cobalt and
Page 642 and 643:
Trifluoromethylzinc compounds prepa
Page 644 and 645:
15.3 Electrochemical Synthesis and
Page 646 and 647:
15.3.2 Carbon±Carbon Bond Formatio
Page 648 and 649:
Cl Cl NC + MeO2C 1eq 2eq e, CoX 2 c
Page 650 and 651:
1eq Br FG + R 2eq OAc e, CoX 2 cat
Page 652 and 653:
Cl O + O e, FeBr 2(Bpy) n DMF, Fe a
Page 654 and 655:
15.4 Electrosynthesis of Compounds
Page 656 and 657:
Page 658 and 659:
FG CuCN/LiCl ZnBr 0ºC CuZnBrCN 15.
Page 660 and 661:
Page 662 and 663:
15.5 General Conclusion (industrial
Page 664 and 665:
17 Durandetti, M.; Devaud, M.; Peri
Page 666 and 667:
I2 Index b-alkoxyalkylidenemalonic,
Page 668 and 669:
I4 Index boronic ester 47 4-boronyl
Page 670 and 671:
I6 Index cyclohexadiene 415 cyclohe
Page 672 and 673:
I8 Index fluoroalkenylstannane 206
Page 674 and 675:
I10 Index iron-catalyzed carbolithi
Page 676 and 677:
I12 Index nickel-catalyzed carbozin
Page 678 and 679:
I14 Index psicosecarbene complexes
Page 680 and 681:
I16 Index Suzuki-Miyaura reaction a
show all

Handbook of Functionalized Organometallics Applications in S

Create successful ePaper yourself

Delete template?

Save as template?