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1.Appel Reaction
CX4, PPh3
X = Cl, Br, I
The reaction between triphenylphosphine and tetrahalomethane (CCl4, CBr4)forms a salt known as Appel’s salt.
Treatment of alcohols with Appel’s salt gives rise to the corresponding halides.
PPh3
+PPh3X, CX3
+
Appel salt
Mechanism
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2.Baylis–Hillman reaction
TEA
X= O, NR2
EWG = CO2R, COR, CHO, CN, SO2R, SO3R CONR2, PO(Et)2
It is a carbon-carbon bond-forming transformation of an electron-poor alkene with a carbon electrophile.
Electron-poor alkenes include acrylic esters, acrylonitrile's, vinyl ketones, vinyl sulfones, and acrolein’s.
On the other hand, carbon electrophiles may be aldehydes, α alkoxy carbonyl ketones, aldimines,
and Michael acceptors.
Example
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3.Boekelheide reaction
TFAA
TFAA = Trifluoroacetic anhydride
Treatment of 2-methylpyridine N-oxide with trifluoroacetic anhydride gives rise to 2-hydroxymethylpyridine.
Hydrolysis
Mechanism
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4. Buchwald–Hartwig Coupling
Pd(OAc)2, dppf,
Base, Toulene
Direct Pd-catalyzed C–N and C–O bond formation from aryl halides and amines in the presence of
stoichiometric amount of base.
Pd(0)
Oxidative
addition
Ligand Exchange Reductive
elimination
Mechanism
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5. Chugaev elimination
1. CS2, NaOH
2. MeI
xanthate
Heat
OCS CH3SH
Alcohol converted to xanthates followed by thermal elimination of xanthates to olefins
Heat
Me-I
Mechanism
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6. Core-Chaykovsky reaction
Coreys ylide
1 2.
1 or 2
X = O, CH2
, NR2, S, CHCOR, CHCO2R, CHCN
The Core-Chaykovsky reaction entails the reaction of a sulphur ylide, either dimethylsulfoxonium methylide
1 (Corey’s ylide) or dimethyl sulfonium methylide 2 with electrophile such as carbonyl, olefin, imine, or
thiocarbonyl, to offer as the corresponding epoxide, cyclopropane, aziridine, or thiirane.
Mechanism
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7.Mitsunobu reaction
NuH
DEAD, PPh3
SN2 inversion of an alcohol by a nucleophile using diethyl azodicarboxylate (DEAD) and triphenylphosphine
:PPh3
DEAD
Adduct formation
H-Nu
Alcohol
Activation
Nu-
Mechanism
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9.Shapiro reaction
-
E+
2 nBuLi
The Shapiro reaction is a variant of the Bamford-Stevens reaction. The former uses bases such as alkyl lithium
and Grignard reagents whereas the latter employs bases such as Na, NaOMe, LiH, NaH, NaNH2, etc.
Consequently, the Shapiro reaction generally affords the less-substituted olefins as the kinetic products, while
he Bamford-Stevens reaction delivers the more-substituted olefins as the thermodynamic products.
nBu-
nBu- -N2 -
E+
Mechanism
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12. Kulinkovich reaction
Ti(iOPr)4
H+
In the Kulinkovich reaction formation cyclopropanols via reaction of esters with dialkyldialkoxytitanium
reagents, generated in situ from Grignard reagents bearing hydrogen in beta-position and titanium(IV)
alkoxides such as titanium isopropoxide