and ketones

chemistry
organic
Protectinggrit
Chapter 19-Aldehydes
weakbases- a

10] -
oH
He
OH
/sola higher priority than ketones
I

(H) Hi,I don /

Weak [H]

ald/ket amines
+
-
ald larger keg
-> less stable
↓
-> more reactive

GIC
why? more part
absence of EBG

Faci
Ho
+ more Iton carbonylc->
better Et

NaBHP:ket,
-
ald, any, acyl

LiAlHe: + ester, amide zoamine Wolff-kishner & Clemmenson reductions -> remove i
,
↓ -

hydration alkynes In, i eeno

g- tnt. H
=> enamine

Ch24

apiecee
conditions =

paniniactinars
acetal formation under acidic acetal

metal
-

o
-11
** (it)
-

on how - > H20

~
cyanide 1

a
+

↑ NaCN

me on
-
- risopro,

-
·natianrear
acids
Chapter 20-carboxylic
amide hydrolysis drives aorable
grig +
202
nota.- esters only under acidic conditions, by
if
orat Does
it

mas
# Mon BUT, can do SN2 with
justdeprof. OH
basic, more favorable to
c.a. as nucleophile 10
nitrile hydrolysis

term in A.A. - CEN Mo-k+o

-- returns in protection of

Fischer ester synthesis ↳

mech=acetal formation basic esterification
irreversible? (,)anrolysis

he
Why is
will favor A/B chemistry
carboxylate
mech NAS chlorides i
saponification
=

acyl

far
e wasteful

-
anhydrides are a
in practice
as re
C.a.
+
SOCI nitrile reduction
-
1
reactive

-on ,highly
-
anhydrides
decarboxylation
acylchlorides ald
to or sterically *-
it i
nindered
hydrides
TN **N
0

I Al
CO2 t
hioester
22 enols & enolates
Chapter stabilized
-

enolate resonance
HYg-coA" INH,HS-COA
exterariamn ost e
both acid & base will racemize a chiral center

hi""
0
-
musthave chiral center (a to carbonyl
amide reductions:odd normally carbonyl0
halogenation & a position A
retained
il LiA& is
more stable
->
acidic
anhydride enolate ~NH2 NH
, henydentalintemediates because see resonances
isto nitrile grig
a.s amide
->

usetie inthe
#
# c.
avoid AlBuxn
to

basic ket
nitrile -imine
-

An
0
is
greatestchangedintermediates
Br malonic ester synthesis (acetoacidic
ester)
condensation

Itdentificatilationdoesite
Br
mixed claisen
acids
halogenating c.
useful method synthesize
to

cracemic)a.a. bestw hen Ie ster has no o-hydrogens

Fif Br e
Eve"toa nmm
I

., . :
ne .

-
- 3-hydroxyaldehyde keepinmaidare more acidic than esters B-dicarbonyl

illr
induction
due to (EDG)
catalystworks
aldolsummantree e
Raisebeamenter
as base
EIcB also LDA
e
n between d.

"*"
-

new alkene

-4 =48?H's
6, -unsaturated
carbonyl

denation,insen
· condensati o n to on
0
-

pka18.7
-

Ire
A automatically addition:using enolate
as Nu

ripped off who atel -> Michael's Robinson annulation

-.
acidic workup Michael's Addition

minitiateemit
0

1 interactcondensation
inan
give cyclohexanone
to

+
Chapter 23-amines Chapter 28-carbohydrates
SNC alkylation can resultin overalkylation
&-anomer glycosidation

mig
&-anomer
homei n
acidic conditions

resi "oct*nomeric
esters
acylation better:anhydrides, acylchl, ia,
man
only

on
0
CH30H
Yor+MNH -

Ha a
trans
&=
conditions
positions
salts
hotmann elimination ofquaternary ammonium basic

isin
⑧ AgzO will favor less
*
run it
*it
crowded alrene
E
reduction

arr reene
CHO meOH

sayminreat
or

to
it "alditol"

on CH2OH

IH, E-Husefulweare tautomerization can use (aCOs

mit-in
also
glucose
AgzO(Tolleris)
are are in
Ar
0 or
functional group
=

HC
↳carboxylate

Art is it
"alderic acid"
reduction of nitro compounds also reduce nitro
x can glucose
&-OH
TN
linkage e

*NO2
~I SnIHCl
(Wolff-Kishner) -aior glycosidic se

minapple aromatic hetrcycles nucleiand

galactose glucose
+ -

acid derivatives
Chapter 25-thioesters
&
phosphoric
loss of phosphate group x
i holding charge
onH e
+

best
depends

- - xadenine
Ms on enzyme blc smallest

Ensin
for which P is
acetyl CoA -
attacked

Is-CoA +
HO-NCCHels , No--NICHals NOH
draw res

acetylcholine
thio-claisen acid synthesis)
(fatty acylphosphates

Nominence,itin
0
0

, all,con-> HiscoAH
0

-co -
Haj H

sits to
glutamate glutamine
reduction of thioester
⑧
LiAle
*

harlesATP+ coupled reactions

30.3k5/mol
I wine at

Il ->
H 4
phosphate
-
=

es ADP
ATP H20 =
+

hisare 1G +13.8 k5/mol if full octet

st
+

H20 Notonly stable

glucose phosphate glUc-b-phos
I
+ =

esters -
phosphate plentiful
+

hydrolysis of
16.7 k5/mol
-

-
0

i Il
dz neut
alkylation
-

OH 3 DNA
j
I
-

Et
+-
->
CH3
0
Eto

NAS tressres! EtoIt" *alogen

OH
-

** *
EtOH ~7

-
subs. only mech
westers, acyl
subs. & SNC work
esters, both acyl
phosphate
beStrongerare
w/ ↳> deoxy

20 & 30
d'tincreasing
hydrolysis sequentially
repulsion
slower
better LG cytosine uracil
=

NH2
I body doesn'trecognize

*
back
DNAphosphodiester
SEE ist",with

stairs C G winner
-

form
mono:unable to polymer
tri:falls aparttoo fast H uracil
"imine"

heresofgaincabbarteningmply,
moment cytosine
large dipole
protein sequencing
protein synthesis
Edman degradation
Ron R-butthis give might gets
PKa-18 PKaw3
c.a. protecting group-ester formation (ch20)
*
/H2O
finding pl basic ↓MezNPh, pyridine
~on He
if side chain Not
- - > to
remotene
pI(acidic) avg. of 2 smaller pKa's
-in
Froc
if side chain acidic
as
=

-
pep

PI(basicarg.of largeramore
2
base
amine protecting groups ="amides" + ↳

synthesis a mino acids

of

6-bromo method

Ro-er,
(same as ch22)
notmethods make racemic a a.
2an howtore -
- ,
o 10

-no miss
amines
PBU3
can only syn

me,
"Foc" a a.
+

HaN remove
synthesis

--
strecker to

win is solid phase synthesis

be automated
process can
↓The rearrange ring
synthesis
aminomalonate (same as malonic ester syn)
Boc-aa.+CICH
-

Nyer base, BOC-a.A.-CHc-Poly S

2out
* areat si
~aretree.
↓
* -

HOCH2-Poly CH2-Poly
I.
(a.a)n a.a.-
+

a
DCC,
↓
wash
box-a a .

HEt boc-(.a7
CH2-Poly
eatyou-aa.-a.a-CHc-Poly proteinstructuree
tRNA
interactions
attaching a a. to 2 backbone
amide groups
enzymes H-bonding between

anishanbaud(a8preatanin
present -pleated sheets
&A-A- based on a.a.
ester syn. function via organic catalysis 2-helix&

air-minracy.Ire Photofractions
a ctive
at site 3
competitive
inhibition:repulsion!
digestine hydrolysis ↑ multiple proteins aggregating
biological protein synthesis

potec e
linkage
newadforms amide
!
an e