Grc`s Collection in Organic synthesis

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Grc`s Collection in Organic synthesis

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� Chromium reagents:

Cr (IV) reagents H2CrO4,HCrO-4,CrO4

-2,HCr2O7,Cr2O7

-2,H2Cr2O7 and H2Cr2O7

- …

Oxidation of alcohol accompanied by reduction of the Cr(VI) to Cr(III)..

� CrO3 in H2O or Aq AcOH:

� CrO3 in acetone with H2SO4(Jones reagent):

� CrO3-Pyridine(Sarett oxidation):

� CrO3-Pyridine-DCM(Collins reagent):

� Pyridinium chloro chromate(Corey`s reagent):

Grc`s Collection in Organic synthesis

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� Pyridinium dichromate:

� 10 Alcohols to 2

0 Aldehydes:

DMSO,Collins, coreys,PDC,Pr4N+RuO4

-,CAN,Na2Cr2O7 in H2O,Hg2CO3-Celite, Hot HNO3 in Aq Glyme,

Cr2Pyridine-CuCl,LTA-pyridine,Benzoyl peroxide-NiBr2..

� DMSO(Di methyl sulfoxide):

S

O

O

� Moffats(DMSO+DCC(dicyclo hexyl carbidoimide)+acid):

OMeO

OSiPh2tBu

OMeO

OSiPh2tBu

OHO

� Dess martin periodinane oxidation:

� Ley Oxidation(tetra propyl ammonium per ruthinate):

� Oppenauer oxidation(Acetone/Al(O i-Pr)3):

� MPV reduction(meerwein pondarf vierly ):

� MnO2: It oxidizes only allylic &benzylic alcohols to their respective carbonyl compounds,

Grc`s Collection in Organic synthesis

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� Fetizon`s reagent(Ag2CO3 on Celite):

20 Alcohols more reactive than 1

0 alcohols.

� Ag2O & AgO:

� KMnO4:

� Phase transfers catalyst(Quaternary ammonium salts):

� Crown ether:

CO2H

O

KMnO4/H2O/Benzene

dicyclohexano 18-crown-6

Grc`s Collection in Organic synthesis

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� Trimethyl silyl iodide:

� Peterson`s synthesis: Beta hydroxyl Trimethyl silane

� 1,3 dithiane`s:

Grc`s Collection in Organic synthesis

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� DCC(di cyclo hexyl carbidoimide):

� DDQ(2,3 di chloro 5,6 di cyano benzo quinone):

Ph

Ph Ph PhO OHO

O OO

O

� Alcoholic H2O2 :

� Mukaiyama reagent(N-Methyl ,2-chloro Pyridinium iodide):

N ClI-

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� RuO4/CCl4 :

� CrO2Cl2:

� H2/Ni :

� Baker`s yeast:

� RMgX :

� Tri n-Butyl tin hydride(nBu3SnH):

R-F < R-Cl < R-Br < R-I

Grc`s Collection in Organic synthesis

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� Gilmans reagent(R2CuLi) :

� LDA(Lithium di isopropyl amide):

Strong base due to 20 amine & free e

- pair. Satirically hindered base

� Wilkinson`s catalyst[Tris (tri phenyl phosphine)rhodium(I)chloride]:

Hydrogenation of C=C, , with out disturbing other functional groups,

It adds H2 to olifins at same side, Cis olefin to meso, Trans olefin to racemic mixture..

� Palladium/H2 :

Grc`s Collection in Organic synthesis

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� H2/Ni useful application:

� Birch reduction:

� Pd-BaSO4(Lindlar`s catalyst):

� Benkeser reduction:

Li0/Et2NH/Me2NH

� Clemmenson`s (Zn-Hg/HCl):

Grc`s Collection in Organic synthesis

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� Wolf kishner reduction(H2N-NH2/KOH):

� With di imides:

� With silanes:

Ph

O3PhMe2SiH

CuF(PPh3)3.EtOHPh

O

� Reduction with HCO2H:

� Sodium boro hydride:

Reduces predominately unconjugated carbonyl compounds.

� Vils meier reaction:

� Silver tetra fluoro borate(AgBF4):

Grc`s Collection in Organic synthesis

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� Luche`s reagent(NaBH4-CeCl3): Reducing conjugating carbonyl compounds,

� Super hydride(LiBHEt3) :

� Sodium cyano boro hydride (NaBH3CN):

Readily reduces iodides, bromides, and tosylates to the hydrocarbons...

HMPA= hexa methyl phosphoramide

� Alanes(AlH3):

� DIBAL-H(Di iso butyl aluminium hydride):

High temperatures: Acid derivatives to Alcohols

Low temperatures: Acid derivatives to Aldehydes

Grc`s Collection in Organic synthesis

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� Adams catalyst (H2-PtO2): Less hindered alkenes to alkanes.

� Rosen mund reduction:

� Fremy`s salt (potassium nitroso di sulphonate) [(KO3S)2NO. ):

Oxidation of phenolic derivatives to quinoids..

� MnO2,DDQ and CAN :

� Uden friends reagent(O2+Fe+2

+ascorbic acid in presence of EDTA):

Gave good yields of ortho and para phenolic derivatives from phenyl acetamide.

� Fenton`s reagent (H2O2+Fe+2): Converts aromatic derivatives in to phenols.

Grc`s Collection in Organic synthesis

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� Elbs persulphate oxidation(K2S2O8/KOH):

� Following reagents can converts the alkenes in to their respective epoxides:

NBS.H2O/NaH, TsCl/Pyridine/K2CO3/MeOH..

Ranking of peroxides:

� Julia colonna epoxidation:

O

Ph

poly-L-Luecine/silica gel

Urea/H2O2/DBU

O

Ph

� Hydrogen peroxide(H2O2):

� Asymmetric epoxidation:

� OsO4-NMO(N-methyl morpholine N-oxide) :

Grc`s Collection in Organic synthesis

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� Wood ward-Prevost hydroxylation’s:

� Baeyer villager epoxidation(CF3CO3H):

� Barbier Wieland degradation:{1)H+,EtOH,2)Excess PhMgBr,3)H3O+,4)CrO3}:2 carbon lost during

the reaction

� LTA(Lead tetra acetate):

� Sodium per iodate(NaIO4):

Grc`s Collection in Organic synthesis

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� Selenium dioxide(SeO2):

� Lithium aluminium hydride(LiAlH4):

� Lithium tri ethoxy aluminium hydride(LiAlH(OEt)3):

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� Red-Al(Sodium bis(methoxy ethoxy )aluminium hydride):

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"Things turn out best for the people who make the best out of the way things

turn out."

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Regards:

Grcvr *~*~*~*~*~*~*~*~*~*~*~*~*~*~*~*~*~*~*~*~*~*~*~*~*~