OChem II U4 Reagents

=O to HO-=C (acid cat tautomerization)

H3O+

=O to HO-= (base cat tautomerization)

-OH

Thermodynamic Enolate

NaOH, more stable

Kinetic Enolate

LDA, less stable

Isotopic Labeling (D)

NaOD / D2O (xs), D at all alpha positions

Acid Halogenation

Br2 (1eq.) / CH3COOH, one Br at alpha position

Base Halogenation

Br2 (xs) / NaOH (xs), Br al ALL alpha positions, may do halform at CH3, replace w/ OH

Aldol Arrow

NaOH / ^OH

Reverse Aldol Arrow

NaOH / ^OH

Claisen Condensation

Enolate + ESTER (3rd ox)

[1]NaOR HOR / [2] H3O+ WKP

Ester LG

1,3 dicarbonyl PDT

Alkylation (new C-C sp³)

At alpha position =O

[1] 1.1 eq. LDA / [2] CH3-I

Alkylation w/ NaOH

Creates reversible enolate, disaster

NaOH / H2O CH3-I

Enamine Alkylation

At alpha =O

[1] R-N-R / HCl (cat)

[2] Ch3-I / H2O HCl (cat)

Malonic Ester (OCOCOCO)

[1] NaOR (match) ROH

[2] R-I

[3] NaOR ROH

[4] R-Br

Hydrolysis + Decarboxylation

[1] NaOH, H2O

[2] H3O+ WKP

or

H2O, H2SO4 (Unit 3)

Create CO2 (both) and only do 1,3 dicarbonyl

Base reactive N

RNH2 HCl → RN+H Cl-

SN2 Style RNH2 attack partial +C

RNH2 RBr → RNRH2+ Br-

Synth of amine via SN2

RNH2 to RNRH

RBr / NaO^=O

Mess of products

Gabriel synth

[1] R-Br KOH

[2] xs NaOH, H2O

Syn 1 prime amine +C

[1] NaCn

[2] LiAlH4 ^O^

[3] H3O+ WKP

ADDS CARBON!

Synth 1 prime amine no extra C

[1] NaN3

[2] LiAlH4 ^O^

[3] H3O+ WKP

Reductive Amination

Acid chloride to RNR

[1] RNH2, PYR

[2] LiAlH4, THF

[3] H3O+ WKP

Reductive Amination

ROR ro RRNHR

RNH2

HCl (cat)

NaBH3BCN

Hoffman rearrangement

LOSE C @ =O

Br2 (1eq)

NaOH, H2O

CREATE CO2, Lots of =

Mannich Reaction C=O to C=C=O

[1] H2=N+CH3CH3 Cl-

H2O HcL

[2] NaOH CH3-I (xs)