Hydroboration and Organic Synthesis: 9-Borabicyclo[3.3.1]nonane (9-BBN) PDF
Preview Hydroboration and Organic Synthesis: 9-Borabicyclo[3.3.1]nonane (9-BBN)
Hydroboration and Organic Synthesis 9-Borabicyclo[3.3.1]nonane (9-BBN) Ranjit S. Dhillon Hydroboration and Organic Synthesis 9-Borabicyclo[3.3.1]nonane (9-BBN) With 196 Figures and 260 Tables 123 Prof. Dr. Ranjit S. Dhillon Department of Biochemistry and Chemistry Punjab Agricultural University Ludhiana-141 004 India e-mail: [email protected] Library of Congress Control Number: 2006935689 ISBN 978-3-540-49075-3 Springer Berlin Heidelberg New York DOI 10.1007/978-3-540-49076-0 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broad- casting, reproduction on microfilms or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution under the German Copyright Law. Springer is a part of Springer Science+Business Media springeronline.com © Springer-Verlag Berlin Heidelberg 2007 Printed in Germany The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Product liability: The publishers cannot guarantee the accuracy of any information about dosage and application contained in this book. In every individual case the user must check such information by consulting the relevant literature. Coverdesign: WMXDesign GmbH, Heidelberg Typesetting & production: LE-TEX Jelonek, Schmidt & Vöckler GbR, Leipzig, Germany Printed on acid-freepaper 2/3141/YL - 543210 This book is dedicated to Prof. Akira Suzuki, Professor Emeritus Hokkaido University, Sapporo Japan Preface Organoborane chemistry expanded very rapidly after the hydroboration pro- cessdevelopedbyNobelLaureate,LateProf.HerbertC.Brown.Organoborane intermediatescanbeconvertedtoalmosteveryclassoffunctionalitypresentin organicmolecules.Thiscontinenthascontributedimmenselyforthewelfareof mankindandiscontinuingtodoso. Among the various hydroborating reagents, 9-borabicyclo[3.3.1]nonane di- mer (9-BBN) has found the most extensive use because of its unique proper- 2 ties, convenient preparation, commercial availability and enormous synthetic applications. Many research papers and some review articles have been published on the synthetic importance of 9-BBN and its derivatives, B-R-9-BBN. However, no singlemanuscriptisavailableontheburgeoningliteratureofB-R-9-BBNforthe convenientaccesstoworkingchemists,teachersandstudents. TheaimofthebookistoprovideorganoboranechemistryofB-R-9-BBNina fast,organizedandillustrated,easilyreadable,andintroductoryfashion. The second aim to prepare this book is to classify a variety of organic reac- tions ofB-R-9-BBN and describethese reactionsin a clear manner so that or- ganicchemistscanuseforthesynthesisofintricatemolecules. Ihopethebookwillstimulatethechemiststoexplore,further,thepotential of B-R-9-BBN intermediates for developing new synthetic methodologies and indesigningorganicsyntheses. Itismyopinionthatorganizationoftopicsof the book will attract advanced organic chemistry students, industrial and aca- demicchemists. IamgratefultoProf.AkiraSuzuki,ProfessorEmeritus,HokkaidoUniversity, Sapporo,Japanwhointroducedmetothissubjectandwithouthishelpitwould nothavebeenpossibletocompletethisbook. IthankProf.S.HaraofHokkaido University,Dr.(Ms.)V.K.Gautam,Dr.(Ms.)Shikha,Ms.Urvashiandmywife Sukhjinder for their help. I also thank Editorial Board of Springer-Verlag for theirhelpandsuggestions. Ludhiana,January2007 RanjitS.Dhillon Contents 1 Introduction .................................................. 1 2 General Remarks .............................................. 3 3 Preparation and Properties .................................... 5 4 Kinetic Studies .............................................. 17 4.1 HydroborationKineticsofAlkenes ........................... 18 4.2 HydroborationKineticsofAlkynes .......................... 27 4.2.1 RelativeRatesbetweenMonohydroborationandDihydroboration ofAlkynes ................................................ 30 4.3 HydroborationKineticsofHaloalkenes ....................... 31 4.4 HydroborationKineticsofHaloalkynes ....................... 38 4.5 ReductionKinetics ........................................ 41 4.6 KineticsofComplexFormation ............................. 48 4.7 KineticsofProtonolysis .................................... 51 5 Hydroboration .............................................. 59 5.1 HydroborationofAlkenes .................................. 59 5.1.1 HydroborationofAcyclicAlkenes ........................... 59 5.1.1.1 TerminalOlefins .......................................... 61 5.1.1.2 InternalOlefins ........................................... 61 5.1.1.3 cisandtransIsomers ....................................... 62 5.1.1.4 Effectofα-MethylSubstituents .............................. 64 5.1.1.5 Effectofα-ConjugatedSubstituents .......................... 65 5.1.2 HydroborationofCyclicAlkenes ............................ 68 5.1.3 HydroborationofChloro-,Acetate-,andAcetal-Functionalized Alkenes .................................................. 73 5.1.4 HydroborationofAllylsilanes ............................... 76 5.1.5 HydroborationofChiralAllylAminesandChiralAllylAlcohols 78 5.1.6 HydroborationofAlkenylheterocycles ........................ 84 5.1.7 HydroborationofEnamines ................................. 96 5.1.8 HydroborationofHeterocyclicOlefins ....................... 99 5.2 HydroborationofAlkynes ................................. 111 5.2.1 Hydroborationof1-Alkynes ............................... 112 X Contents 5.2.2 Hydroborationof1-Silyl-2-Alkyl-1-Alkynes .................. 116 5.2.3 Hydroborationof1-Halo-1-Alkynes ........................ 120 5.3 HydroborationofDienes .................................. 126 5.4 HydroborationofAllenes .................................. 130 5.5 HydroborationofEnynesandDiynes ....................... 136 6 Synthesis of Alcohols ....................................... 143 6.1 SynthesisofSaturatedAlcohols ............................. 143 6.2 SynthesisofAllylicAlcohols ............................... 153 6.3 SynthesisofHomoallylicAlcohols .......................... 155 6.4 SynthesisofPropargylicAlcohols ........................... 163 6.5 SynthesisofHomopropargylicAlcohols ..................... 166 6.6 SynthesisofSilylAlcohols ................................. 172 6.6.1 SaturatedAlcohols ........................................ 173 6.6.2 AllylicAlcohols .......................................... 175 6.6.3 HomoallylicAlcohols ..................................... 177 6.6.4 HomopropargylicAlcohols ................................ 179 6.6.5 DiyneAlcohols ........................................... 180 6.6.6 EndiyneAlcohols ......................................... 181 6.6.7 DiendiyneAlcohols ....................................... 181 6.6.8 AllenicAlcohols .......................................... 183 6.6.9 AlleneneAlcohols ........................................ 186 6.6.10 AllenyneAlcohols ........................................ 187 6.6.11 AllendienyneAlcohols .................................... 188 6.7 SynthesisofHeterocyclicAlcohols .......................... 188 6.8 SynthesisofAminoAlcohols ............................... 193 6.9 AsymmetricSynthesisofAlcohols .......................... 194 7 Synthesis of Aldehydes and Ketones ....................... 213 7.1 SynthesisofAldehydes .................................... 213 7.2 SynthesisofKetones ...................................... 219 7.2.1 SynthesisofSaturatedandAromaticKetones ................. 219 7.2.2 SynthesisofEnones ....................................... 227 7.2.2.1 Synthesisof(E)-β-γ-Enones ................................ 227 7.2.2.2 Synthesisofγ,δ-Enones ................................... 227 7.2.3 Synthesisofγ,δ-Ynones ................................... 229 7.2.4 SynthesisofDienones ..................................... 231 7.2.5 SynthesisofConjugatedEnynones .......................... 231 7.2.6 Synthesisofβ-Ketosilanes ................................. 233 7.2.7 Synthesisof1-Metallacyclohexan-4-ones .................... 233 7.2.8 SynthesisofChiralKetones ................................ 234 8 Synthesis of Carboxylic Acids ............................... 237 8.1 SynthesisofUnsaturatedAcids ............................. 237 8.2 Synthesisofβ-AminoAcids ................................ 237 Contents XI 9 Synthesis of Esters ......................................... 241 9.1 SynthesisofAchiralEsters ................................. 241 9.2 SynthesisofChiralEsters .................................. 242 9.3 Synthesisof(E)-β,γ-UnsaturatedEsters ...................... 246 9.4 Synthesisofα-AminoAcidEsters ........................... 248 10 Synthesis of Nitriles ........................................ 253 10.1 SynthesisofAchiralNitriles ................................ 253 10.2 SynthesisofChiralNitriles ................................. 255 10.3 Synthesisof(E)-β,γ-UnsaturatedNitriles .................... 257 11 Synthesis of (E)-β,γ-Unsaturated Amides ................... 259 12 Synthesis of Amines ........................................ 261 12.1 SynthesisofChiralAmines ................................ 261 12.2 SynthesisofHomopropargylicAmines ...................... 266 12.3 SynthesisofSecondaryAmines ............................. 267 13 Synthesis of Halides ........................................ 271 13.1 SynthesisofHalidesviaHydroboration ...................... 271 13.2 SynthesisofHalidesviaHaloboration ....................... 273 13.2.1 Synthesisof2-Halo-1-Alkenes .............................. 273 13.2.2 Synthesisof(Z)-1-Alkynyl-2-Halo-1-Alkenes ................ 276 13.2.3 Synthesisof(Z)-δ-Halo-γ,δ-UnsaturatedKetones ............. 277 14 Synthesis of Dialkylsulfides ................................. 283 15 Synthesis of Thiophene Oligomers ......................... 285 16 Synthesis of Cyclopropanes and Cyclobutanes ............. 287 17 Synthesis of Borinanes ..................................... 291 18 Synthesis and Transformations of Butterflyboranes: cis-Bicyclo[3.3.0]oct-1-yldialkylboranes .................... 297 19 Synthesis of α-Bromoboranes .............................. 303 20 Synthesis of Borinates ...................................... 307 20.1 EnolBorinates ........................................... 307 20.1.1 Synthesisof(E)-and(Z)-EnolborinatesfromSaturatedKetones 307 20.1.2 StereoselectiveSynthesisof(Z)-EnolBorinatesfromα,β- UnsaturatedKetones ...................................... 312 20.1.3 SynthesisofStablecis-B-Vinyl-9-Oxa-10-Borabicyclo[3.3.2]decane (cis-B-Vinyl-OBBD)Derivatives ............................ 313 XII Contents 20.1.4 SynthesisofStabletrans-B-Vinyl-9-Oxa-10- Borabicyclo[3.3.2]decane(trans-B-Vinyl-OBBD) ............. 314 20.1.5 MarkovnikovVinylborinates:SynthesisofB-Vinyl-9-Oxa-10- Borabicyclo[3.3.2]decane(Vinyl-10-OBBD) .................. 314 20.2 SynthesisofAlkynylborinates .............................. 316 21 Synthesis and Transformation of Polymers ................. 321 22 Synthesis of Alkali Metal 9-Boratabicyclo[3.3.1]nonane (Li, K, and Na 9-BBNH) ...................................... 323 23 Synthesis of B-R-9-BBN Not Available via Hydroboration ... 327 24 Synthesis of Unsaturated Compounds ...................... 337 24.1 SynthesisofAlkenes ...................................... 337 24.1.1 SynthesisofAcyclic,Cyclic,andHeterocyclicAlkenes ......... 337 24.1.2 Synthesisof(Z)-Alkenylsilaneand(Z)-Alkenyltin ............. 347 24.1.3 Synthesisof(Z)-1-Halo-1-Alkenes .......................... 351 24.2 SynthesisofDienes ....................................... 352 24.2.1 Synthesisof1,ω-Dienes ................................... 352 24.2.2 SynthesisofInternal1,3-Dienes ............................ 361 24.2.3 SynthesisofNitrogen-ContainingHeterocyclic(Z)-1,3-Dienes .. 364 24.2.4 SynthesisofSulfur-Substituted1,3-Dienes ................... 366 24.2.5 SynthesisofStannylDienes ................................ 368 24.2.6 SynthesisofB-IsoprenylDerivatives ......................... 369 24.3 SynthesisofEnynes ....................................... 370 24.3.1 StereoselectiveSynthesisofConjugated(E)-and(Z)-Enynes .... 370 24.3.2 StereoselectiveSynthesisofSilylated(E)-and(Z)-Enynes ...... 371 24.4 SynthesisofEndiynes ..................................... 373 24.4.1 StereoselectiveSynthesisof(E)-and(Z)-Endiynes ............ 373 24.4.2 StereoselectiveSynthesisof(E)-and(Z)-SilylatedEndiynes .... 373 24.5 Synthesisof5-Methylene-1,3-Cyclohexadienes(o-Isotoluenes)and 1,2,4,6-Heptatetraenes:(Diene-Allenes) ..................... 375 24.6 SynthesisofEnyne-Allenes,Dienyne-Allenes,andTrienyne- Allenes,andTheirCycloisomerization ....................... 376 24.7 SynthesisofSilylatedZ,Z-DiendiynesandZ,Z,Z,Z- Tetraentetraynes,andTheirCycloisomerization .............. 381 25 Reduction .................................................. 397 25.1 With9-BBN·THF ......................................... 397 25.2 With9-BBN·Py .......................................... 408 25.3 WithLi9-BBNH ......................................... 410 25.4 WithB-Siamyl-9-BBN .................................... 414 25.5 WithLithium9,9-Di-n-Butyl-9-Borabicyclo[3.3.1]nonanate .... 415 25.6 With9-BBNDerivatives(asCatalysts) ....................... 422 Contents XIII 26 Asymmetric Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427 26.1 Alpine-Borane ........................................... 428 26.1.1 ReductionofAldehydes ................................... 428 26.1.2 ReductionofKetones ..................................... 433 26.1.2.1 ReductionwithAlpine-Borane,underPressure ............... 433 26.1.2.2 ReductionwithAlpine-BoraneasNeatorinExcess ........... 437 26.1.2.3 ReductionofProchiralKetones ............................. 437 26.1.2.4 Reductionofα-Haloketones ............................... 441 26.1.2.5 ReductionofKetoesters ................................... 442 26.1.2.6 Reductionofα,β-UnsaturatedKetones ...................... 444 26.1.2.7 ReductionofPropargylKetones ............................ 445 26.1.2.8 ReductionofPropargylicKetoneswithα-ChiralCenters ....... 449 26.1.2.9 ReductionofAcylcyanide .................................. 451 26.2 NB-Enantrane ........................................... 452 26.3 Eapine-BoraneandPrapine-Borane ......................... 453 26.4 NB-Enantride ............................................ 459 26.5 Eapine-Hydride .......................................... 461 26.6 K-Glucoride ............................................. 462 26.7 K-Xylide ................................................ 468 26.8 K9-OThx-9-BBNH ....................................... 472 26.9 LithiumDi-n-ButylAteComplexof9-BBN .................. 473 26.10 Li9-BBNH .............................................. 475 26.11 ComparativeDataofAsymmetricReducingAgents ........... 476 27 Cleavage of Ethers ......................................... 487 28 trans-Metalation ........................................... 491 29 Separation of Isomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499 30 Diels-Alder Reaction ....................................... 501 31 Suzuki Reaction ............................................ 523 31.1 MechanismoftheSuzukiCatalyticCycle .................... 554 32 Miscellaneous Reactions ................................... 559 Subject Index ....................................................... 573
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