[PDF] Organic Chemistry-III CH-423



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Organic Chemistry-III CH-423

CH423&Course&on&Organic&Synthesis;&Course&Instructor:&KrishnaP &Kaliappan& CH-423 (2013)/Chem/IIT-B Dr Kaliappan, Krishna P Organic Chemistry III Classification of reactions: A brief introduction to substitution, elimination, addition, oxidation, reduction, rearrangement and pericyclic reactions



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Krishna P. Kaliappan Department of Chemistry Indian Institute of Technology-Bombay Mumbai 400 076 INDIA http://www.chem.iitb.ac.in/~kpk kpk@iitb.ac.in

9/3/14

Organic Chemistry-III CH-423

Syllabus

CH-423 (2013)/Chem/IIT-B Dr. Kaliappan, Krishna P. Organic Chemistry III Classification of reactions: A br ief introductio n to substitution, elimination, addition, oxidation, reduction, rearrangement and pericyclic reactions. Functional group transformations: alcohols to alkylat ing agents, Mitsunobu and related reactions, introduction of functional groups by nucleophilic substitution at saturated carbon, nucleophilic cleavage of C-O bonds in ethers and esters an d inter-conv ersion of carbox ylic acid derivatives. Oxidation: Metal based oxidizing reagents: A review and detailed discussion of chromium, manganese, ruthenium, silver and other metal-based reagents. Non-metal based oxidizing reagents: D MSO, peroxide, peracid and oxygen based oxidation. Miscellaneous oxidizing reagents like IBX, DMP, CAN, DDQ, periodate etc.

Syllabus

CH-423 (2013)/Chem/IIT-B Dr. Kaliappan, Krishna P. Organic Chemistry III Reduction: Homogeneous and heterogeneous hydr ogenations; Discussion on borane b ased racemic and c hiral reagents, aluminum, tin, silic on based reducing agents. Dissolving metal reductions. Selectivity and protec ting groups: Illustration of chemoselectivity, regioselectivity and stereoselectivity wi th examples; p rotecting groups for alcohols, amines, acids, ketones and aldehydes. Cycloaddition reactions: Diels-Alder reaction; general features, dienes, dienophiles, selec tivity, intramolecular and intermolec ular reactions, hetero-Diels Alder reaction. 1,3-dipolar cycloaddition reactions; general features, dipoles, dipolarophiles. [2+2] cycloaddition reactions; general features, selected examples. Molecular rearran gements: Illustration of electron deficient and electron rich skeleta l rearrangements with examples; Sigmatropic rearrangements-Claisen and related rearrangements, Cope and oxy-Cope rearrangements; 2,3-sigmatropic rearrangements and ene reaction.

Syllabus

Suggested Books/Reviews: Jerry March, "Advanced Organic Chemistry", Fifth Ed., Wiley, 2007. F. A. Carey and R. J. Sundburg, "Advanced Organic Chemistry, Part B", Fifth Ed., Springer, 2007. J. Clayden, N. Greeves, S. Warren and P. Wothers, "Organic Chemistry", First Ed., Oxford University Press, 2001. W. Carruthers, I. Coldham , "Modern Methods of Organic Synthesis", Cambridge University Press K. Peter C. Vollhardt and Neil E. Schore "Organic Chemistry" W. H. Freeman and Company, 1999. Evaluation Pattern Mid-Semester 30% End Semester + Assignment 50% Quiz (2) 20% -There will be a total of 36 (1h) lectures, and 7 tutorials

Functional Groups

Only With Carbon and Hydrogen

CCCC

With Heteroatoms

With One Oxygen Atom: 1. Alcohol: 2. Ether:

ROHPrimaryalcoholOHRRsecondary alcoholROHRRtertiary alcoholODiethyl etherOanisoleOdiphenyl ether

Functional Groups

5. Epoxide, Cyclic Ethers: 4. Aldehyde: 3. Ketone:

With One Oxygen Atom:

Functional Groups

With Two Oxygen Atoms: With Heteroatoms 1. Acid:

OHOAcetic acidOHOBenzoic acid

2. Ketal:

RROR'OR'

3. Acetal:

RHOR'OR'

4. Ester:

OEtOEthyl acetateOOEthyl benzoate

Functional Groups

With Two Oxygen Atoms: 6. Peroxides: With Three Oxygen Atoms: 1. Anhydrides: With heteroatoms 5. Lactones (Cyclic Esters):

OOγ-lactoneOOδ-lactoneROOROOOAcetic anhydride

Functional Groups

With Three Oxygen Atoms: 3. Peracids: With Heteroatoms 2. Hydroxy acids: OOHOHOOHOHOOHOHγ-hydroxy acidβ-hydroxy acidα-hydroxy acidOOOHClmeta-chloro perbenzoic acid

Functional Groups

With Heteroatoms 1) Amines: With One Nitrogen Atom

H3CNH2H3CHNCH3NMethyl amine(primary amine)Dimethyl amine(secondary amine)Triethyl amine (tertiary amine)

2) Aromatic Amines:

NH2Aniline

3) Nitriles:

H3CCNAcetonitrile

Functional Groups

4) Aziridines: With Heteroatoms With One Nitrogen Atom

HNaziridine

5) Aromatic Amines:

NNHPyridinePyrrole

6) Imines:

RHNHPrimary aldimineRHNRSecondary aldimineRRNHPrimary KetimineRRNRSecondary Ketimine

Functional Groups

With Heteroatoms With Two Nitrogen Atoms

H2CN2Diazomethane

1) Diazo:

NNRR

2) Azo:

NNBenzenediazonium cation

3) Diazonium: With Three Nitrogen Atoms 1) Azides:

RNNNNNHNNNHN1,2,3-triazole1,2,4-triazole

2) Triazole:

NNNHN1-triatrazole

1) Tetrazole: With Four Nitrogen atoms

Functional Group

With Heteroatoms With One Nitrogen Atom and One Oxygen Atom 1) Amides: 2) Lactams:

3) Oximes: 4) Nitroso: 5) Nitrile Oxides:

Functional Group

With Heteroatoms With One Nitrogen Atom and Two Oxygen Atoms 1) Nitro: 2) Nitrones:

RNO2NORR

With Two Nitrogen Atom and One Oxygen Atom 1) Urea:

H2NNH2O

Functional Group

With Heteroatoms (Sulfur) 1) Thiols:

SHSHThiophenolEthanethiol

2) Thio Ethers:

RSR

3) Thio carbonyl:

RRSS

4) Thiirane: 5) Heterocycles:

SThiophene

Functional Group

With Heteroatoms (Halogens) 1) Halides: 2) Halohydrin: 3) Dihalides: 4) Acid Chloride: 5) Halolactones:

H3CIBrMethyl iodideEthyl bromideHOClROHRIClCl1,2-dichloroethaneClOAcetyl chlorideOOI

Functional Group Transformations

OrganicSynthesis and Music: What is Common Between Them? Reactions Can be Classified into Seven Types Elimina'onOxida'onPericyclic

Functional Group Transformations

1. Addition Reaction: a. Nucleophilic Addition

RR'ONuRR'ONuERR'OENu

Reaction is categorized by first step and not by second step b. Electrophilic Addition

Br2BrBrBrBrX.X.Y.YX

c. Radical Addition

Functional Group Transformations

2. Elimination Reactions E

1 , E 2 , E 1CB , syn, anti, pyrolytic

OAcOOHAcOHOAcHAcOHSyn eliminationOHNaHCS2, MeIOHH

Side reactions like Wagner-Meerwein rearrangement can take place Syn Elimination:

OSMeSHXanthate ester

HSSMeOCOS + MeSH

Functional Group Transformations

3. Substitution Reactions a. Aromatic Substitution b. Aliphatic Substitution 1. Nucleophilic Substitution S

N 1, S N 2, S N i 1. Nucleophilic Substitution

FNO2ORNO2OR

2. Addition- Elimination

CNBrNaNH2CN

via Benzyne 2. Electrophilic E1, E2, E1CB, syn, anti, pyrolytic

Base must be non nucleophilic

NHOHOOMorphine (Acute pain killer)Ac2OH+NAcOAcOOHeroin

Functional Group Transformations

Esters Ways to make esters

ROOHCH2N2ROOMeROOHH2CN2ROOH3CN2

If compound containing nitrogen having more nitrogen content (more than 50%), then compound may be explosive (CH

2 N 2 is explosive) OHCH2N2OMeROHCH2N2ROMeProton must be acidic enough to pick by CH2N2OHOHCH2N2OHOMe

Ways to Make Esters

Functional Group Transformations

R'-IRCO2H+RCO2R'baseR'OHRCO2H+RCO2R'DCCNCNN,N'-Dicyclohexylcarbodiimide (DCC)NCNROOHR'OHHNCNOORRCO2R'NHONHDicyclohexyl urea

+ Sometimes its difficult to separate product from DCU, in that case, use EDCI instead of DCC

Functional Group Transformations

Ways to Make Esters

Baeyer-Villiger Oxidation

OOOmCPBA

Favorskii Rearrangement

OBrCO2EtNaOEt/EtOH

MitsunobuReaction

R'OH+RCO2HDEAD, PPh3RCO2R'NNCO2EtEtO2CPh3PNNCO2EtEtO2CPh3POROHNNHCO2EtEtO2CPh3PROHRCO2+ROORCO2R'OPPh3+HNNHCO2EtEtO2C+ROPPh3

Functional Group Transformations

Ways to Make Esters

Mitsunobu Reaction

RR1OHPPh3, DIADR2CO2HRR1OR2ONNCO2RRO2CR = iPr, DIAD Diisopropyl azodicarboxylateR = Et, DEADDiethyl azodicarboxylateOOOBnO?OOOBnOH+, H2OHOOBnOOHOPPh3, DEAD

Functional Group Transformations

RR1OHPPh3DEADOHRR1OPh

26

Functional Group Transformations

Mitsunobu Reaction

Nitrogen Nucleophile:

OBnOHPPh3, DEADTsNHCH3OBnNTsH3CNHNOPPh3DEADOHNNO

Intramolecular Mitsunobu Reaction:

HNHOCO2EtCO2EtPhPPh3DEADNCO2EtCO2EtPh

Weak Nitrogen Nucleophile:

OBnOOBnOHBnONHRPPh3, DEADOBnOOBnBnONR

27

Functional Group Transformations

Mitsunobu Reaction

Azides:

ROH + PPh3 + DEADHN3PPh3 +ROHNHNCO2EtEtO2CRN3RN3 + Ph3PONNCO2EtEtO2CPPhOOPhOHO(PhO)2PN3

Can be used instead of HN

3

NNCO2EtEtO2C(PhO)2PN3OPPh3NNCO2EtEtO2CPPhOOPhOPPh3OHRNNCO2EtEtO2CPPhOOPhOHROPPh3+NNNRN3 + PhPOO(PhO)2PN3ROH ++ PPh3 + DEAD

Alcohols

Reduction: Primary alcohols

RNaOH, H2O2BH3ROHHCHORMgXRCH2OHRCHONaBH4RCO2RLiAlH4RCO2HLiAlH4

Functional Group Transformations

Secondary Alcohols

RR'OreductionRCHORMgXROxymercurationRMgXHCO2Rsymmetrical 2o alcohol formate ester

Tertiary Alcohols

RR'ORMgXROxymercurationRMgXRCO2R

Functional Group Transformations

Alcohols

ROHPyridine, MsclROMsMesylateROHPyridine, TsclROTsTosylateROHPyridine, BrclROBsBrosylateROHPyridine, NsclRONsNosylateROHPyridine, Tf2OROTfTriflateROTsNaBrAcetoneRBr

Finkelstein reaction

Alcohols are important class of compounds but they are not good leaving group xOH is not a reactive alkylating agent. Reactivity can be enhanced by converting into a better leaving group like sulfonate esters or halides Most reactive

Functional Group Transformations

Activation of Hydroxyl Group

Preparation of Sulfonate Esters:

ROHClSOClOSOClRCl

Functional Group Transformations

Preparation of Alkyl Halides:

RCl++SO2Cl

Alkyl halides are involved in the formation of C-C bond by nucleophilic substitution

Inversion of configuration

But, if reaction is taking place in solvent like 1,4-dioxane

OSOClROOOORClRCl

Retention of configuration

Reaction with SOCl

2

Activation of Hydroxyl Group

PClClRO2ROHPORORRO

Functional Group Transformations

PClClClROH

Reaction with Phosphorous Halides

- HCl The reaction will stop at this stage if it is carried out in presence of an amine

PORORROH+

When amine is not present

POROROHClR2RCl+POHOHOH

Inversion of configuration

Drawbacks: Not suitable for acid sensitive compounds Amines can not be used

OHOOBrOO?RClPHOROR+O

Activation of Hydroxyl Group

Ph3PBrBrBrPh3PBr+ROHROPPh3Br- HBr

Reaction with Alkoxyphosphonium Salts

RBrOPPh3

Formation of strong phosphoryl double bond is the driving force

HOPh3PBr2BrROHPPh3+RBrOBrBrBrBr

+Bromide source

Functional Group Transformations

Activation of Hydroxyl Group

PPh 3 / CCl 4

CCl3ROHPh3PClRCl

Hexachloroacetone can be used as chloride source

PPh 3 / I 2 / Imidazole

NNHI2ROHPPh3RI

Functional Group Transformations

Ph3PIIPh3PIRHO-HIImidazoleROPPh3IRI

Activation of Hydroxyl Group

Functional Group Transformations

Reaction with 2-Halo-3-alkylbenzoxazolium Cation

ONClRHOAdditionEliminationONORClONORCl

Mitsunobu Reaction

Activation of Hydroxyl Group

HBrBrBrOBrBrHBrHBrOHBrHOBrHBrH2OBrBrBrBr

Functional Group Transformations

Mild Method

OHMsClPyOMsLiClClMsOLi

Some Other Methods

OO

Activation of Hydroxyl Group

Functional Group Transformations

Nitriles

DehydrationRCONH2AbnormalBeckmannRearrangementNROHRCNLAHH2/ Pd-CRCH2NH2H3O+RCO2HR'MgBrRCOR'DIBAL-HRCHO

RX + NaCN

AlkylationR'R'CN

Functional Group Transformations

Preparation of Nitriles

RXNaCNRCNRONH2P2O5RCN

aldoxime Beckmann rearrangenment can also occur Reaction proceed faster in polar aprotic solvents

NHONH2OH+NHNOH2ONOHNOH2NNCH+

tertiary carbocation -H+RNHOHp-TsCl, PyAcCl, PyRCN

Functional Group Transformations

Preparation of Nitriles

RCH2Br + KCN18-Crown-6CH3CN83oC

RCH 2 CN

RCHOROHCN

stable under mild acidic condition unstable under basic condition

OH-RCHO+CN-RCHOROTMSCNKCNH+TMSCNZnBr2

RCNR'MgBrH+/H2OROR'RCNLDAR'IRCNR'RCNRCNRCNRCNLAHorH/Pd-CRCH2NH2partial hydrolysisRONH2H3O+RefluxRCO2HSnCl2/HClDIBAL-HROH

Stephen reaction

Utility of Nitriles

Functional Group Transformations

Functional Group Transformations

Azides

RN3NFN3ROHPPh3, HN3DEADROHP(OPh)2ON3DBUROHH2/ Pd-CRNH2PPh3, H2ORNH21,3-DipolarcycloadditionNNNRNaN3, DMSOR'CH2BrR'CH2BrNaN3, PTC

RXNaN3, DMFRN3RN3PPh3, DEADHN3ROH

Preparation of Azides

Functional Group Transformations

RCH2BrNaN3TBAB25oC

RCH 2 N 3 At room temperature & phase transfer condition: From alcohols: Mitsunobu Reaction

NFHORMeNOMeRNOMeRN3 +ROH(PhO)2PN3ODBURN3

1,8-Diazabicycloundec-7-ene

NNDBUN3

Utility of Azides

Functional Group Transformations

RN3H2/Pd-CRNH2PPh3, H2ORN3RNH2

Staudinger Reaction

Preparation of Amines

With same number of carbon atom

Gabriel amine synthesis

Functional Group Transformations

Amines

NOOK

With One Carbon Atom More

With One Carbon Atom Less

RNH2ORNH2RN3OROHORNH2RNH2

Hoffmann Rearrangement Curtius Rearrangement Lossen Rearrangement Schmidt Rearrangement RNH2

Functional Group Transformations

Preparation of Amines

RNHOOH

Functional Group Transformations

Reduction:

Can be achieved by using either one of the reagents

RNH2RH2CNH2RNO2

H 2 / Pd-C LAH Zn/ HCl RCN H 2 / Pd-C BH 3 NaBH 4

LAH Li/ NH

3

RN3RNH2

H 2 / Pd-C B 2 H 6 NaBH 4 PPh 3 , H 2 O

NR'ROHNH2R'R

H 2 / Pd-C LAH Raney Ni

ONRR'R"NRR'R"

H 2 / Pd-C B 2 H 6 LAH

Preparation of Amines

How to Get Secondary and Tertiary Amine ?

RNCreductionRNHCH3

Reaction is not facile

ROR'NH2NaBH4RNHR'

Secondary amine

One pot

Functional Group Transformations

RNR'Schiff baseR''NH2RNR''Schiff baseR'

Synthetic Utility of Amines

RNH2NaNO2HClRN2ArN2ArXX= Br, CN, I

Sandmeyer reaction

RNH2CNRNCNCNRNH2R'CHORNR'

Functional Group Transformations

Amides

RONHR'DCCRONHR'ROClHNOMeMe+

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