Chem Unit 2 Ch 10

stopping the oxidation of an ester at an aldehyde

use Dibal-H with H3O+

Dibal-H is a reducing agent that turns esters into aldehydes

using dess martin periodinane

to turn a primary alcohol into an aldehyde

using Dibal-H with a nitrile group

forms an imine intermediate! PRODUCES AN ALDEHYDE

making ketones via

ozonolysis and acid chloride

ozonolysis to make ketone

pie bond to CH2 and replace with pie bond O

other Ch2 from pie bond also forms pie bond with O

making a ketone with acid chloride

react acid chloride with gillman reacent to make ketone! (R group) of gillman is added to compound and Cl is kicked off

Gillman reagent

(Ch3)2Cu-Li+

replace X with Ch3 (R group)

KMnO4/H20 reaction with aldehyde

KMnO4 oxidizes an aldehyde to a carboxylic acid with presence of water

Organolithium reagents

R-Li is very strong base

ex. R-Br + 2Li → R-Li + LiBr

LiBr is carbanion!!!

Organometallic Coupling reactions and gillman reagents

generic:

this forms a gillman reagent! (use whatever R group you want)

stability of particles

carbocations: 3 > 2 > 1

radicals: 3 > 2 > 1

carbanions: 1 > 2 > 3

negatively charged nucleophiles

-OH, H-, R3C-, RO-, NtirpleC-, -CtripleC-R

neutral nucleophiles

HOH, ROH, H3N, RNH2

hydrating carbonyls

with H20

aldehydes are

more likely to hydralyze because they have a greater net + charge

hydration is

base or acid catalyzed

the catalyst that started the reaction comes out unchanged

under basic conditions

a negatively charged nucleophile adds to the carbonyl group, giving an alkoxide ion intermediate. alkoxide intermediate takes H from H2O, makes compound with 2 alcohol groups

under acidic conditions

protonation of the carbonyl group happens first, then neutral nucleophile is added and subsequent deprotonation occurs

H3O catalyzer emerges unchanged

cyanohydrin formation

ex. catalyst that started reaction comes out unchanged

nucleophilic addition

cyanohydrin reaction with LiAlH4, THF

make a primary amine

cyanohydrin reaction with H3O+

make a carboxylic acid

Pinner reaction

this yields a pie bond to N and a + charge on N, R OH adds to C in C pie N

then react with water to replace pie N+ with O pie!

yields an ester

Imine formation with 1’ ketone

react 1’ ketone with H2N-CH3

Eamine formation

if alpha carbon is avaliable

double bond on more substituted side!

makes alkene bond!

when to form imine vs. eamine

1’ amine (reagent) = form an imine

2’ amine (reagent) = form an eamine