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Transcript of Synthesis - Organic Chemistry Notes at Examville.com
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8/9/2019 Synthesis - Organic Chemistry Notes at Examville.com
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A N D T O T A L
S YN THESIS
12 3. 7 02
S T E R E O S E L E C T IV E
gar e t h j r ow la nds
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j
w h y d o w e n e e d T o ta l S y n th e s is ?
Wsiegmund@wikimedia commons
O
AcO
H
OH
OBzOH
O
O
OH
Ph
BzHN
AcO O
AcO
taxol
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Trois Ttes (TT)@Flickr
NH
H
O O
N
O
O
A s ym m e t ricS yn t he s is ?
w h y d o w e n e e d
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s yn thes is o f p u ree n a n t io m e r s im p or tant
NMe2
Me
P hO
Et O
n ov r adco ugh-s up pr e ss an t
Me2 NMe
P h O
Et
O
da r v onp a in k ille r
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natashalcd@Flickr
c ou r s e o u t lin e
6 lec turesa s ym m e t ric s yn the s is
6 lec turesto ta l s ynthe s is
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c o u r s e n o t e s
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recommended
books
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r
F EA T U R EA R T I C L E
Tos h i fum i Do h iand Yas
u yu k i K i ta
H yper va len t iod ine reag
en ts as a ne w
en trance to organoca ta
l ys ts I S S N1 35 9 - 7 3 4
5 C O MM U N I CA T I O N
Nor i fum i Fu j i ta, Se ij i S h i
n k a ie t a l.
An organoge ls ys tem ca
n con tro l t he
s tereoc hem ica l course o
f an t hracene
p ho tod imer i za t ion
1 35 9 - 7 3 45( 2 0 0 9 )1 6;1
- 0
w w w. rsc.o rg/c he mco
m m
Num ber 1 6 | 2 8 Apr i l 2
0 0 9 | Pages 2 05 3 2 2 2 4
C he m ica l Co m m u n ica
t io ns
, r .r
r .r ,
. . ,
, .
r r r
r r
r r
r r -r
r r
r r
r r
r
r r -
r r r
r r
r
F E T URE RT ICLE
Toshifumiohi and Yasu
yuki Kita
ypervalen tiod ine reage
nts a s a new
entr ance to organ ocatalyst
s ISS1 35 9-7 345 C MM UNIC
TI N
or i fum i Fuji ta, Se iji S hink
ai et a l.
n organogelsystem canco
ntro l the
stereochem icalcourse o
fant hracene
pho tod imer ization
1359 -73 45(2 00 9)16;1- 0
ww w.rsc.o rg/c hem com
m
umber 1 6 | 2 8 pril 2 009 | Pages
205 3 22 24
C he m ica lCo m m u n ic
a t io ns
w w w .r s c .o r g / o b c
V o l ume 7 | N umb e r 9 | 7 M ay 2 0 0 9 | P ag e s 17 37 19 8 8
C O M M U N I C AT I O N J e nni f e r R . H i s c o c k e t a l .F l u o r e s c e nt c ar b az o l y l u r e a ani o n r e c e p t o r s
14 7 7 - 0 5 2 0 ( 2 0 0 9 )7 : 9 ; 1- 6
journa ls
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lec ture oneterminology
s ub s t r a t e c o nt r o land
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chira l ob jec t
non-s upe r pos able
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chira l ob jec t
non-s upe r pos able
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OH
O
HS
NH 2H
HO
O
SH
H 2 N H
chira l com pounds
non-s upe r pos able
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OH
O
HS
NH 2H
HO
O
SH
H 2 N H
chira l com pounds
enant iom er s
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a c hir a l ob ject
s u p e rp o s a b le
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a c hir a l compounds
s u p e rp o s a b le
H OH
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a c hir a l compounds
s ym m e tr y
p la n e of Me Me
H OH
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na m ing:
123.202s
e e
CH 3HO
O
H NH 2
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CH 3HO
O
H NH 214
23
na m ing:
prio ritie s
groups CH 3 NH 2 H CO 2H
1st atom C N H C
2nd atom H, H, H O , O, O
priority 3 1 4 2
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na m ing:low e s t pr ior ity
points aw ay
CH 3HO
O
H NH 2
H 3 COH
O
HH 2 N
14
2
3
1 4
2
3
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1
23
1
2 3
na m ing:
Santiclockwise Rclockwise right
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NH 2
H 3 C CO 2 HH 3 COH
O
HH 2 N1
4
23
1
23
SSna m ing:
fina lly... ( S )-2-a m inopropanoic a c id
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P
O
OMeMe
H Ph
NS
O
t -Bu
N
N
Ru
N
N
N
Nnon-car bon-based
chir a l compounds
princ ipa lss am e
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chira li t yo fother f or m s a x i a l
O
O
O
O
O
O
O
O
MonkeyBoy69@ickr
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chira li t yo fother f or m s
mugley@ickr
PPh 2
PPh 2
Ph 2 P
Ph 2 P
a x i a l
h
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chira li t yo fother f or m s h e l i c a l
P [8]helicene M [8]helicene
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chira li t yo fother f or m s
plan a r
Fe PPh 2
Ph
FePh 2 P
Ph
ore
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compounds w i t h
enantiom ers
s te r eocentr e s2or more
OH
NH 2
OH
NH 2
ore
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compounds w i t h
dia s te reois om ers
s te r eocentr e s2or more
OH
NH 2
OH
NH 2
OH
NH 2
OH
NH 2
more
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compounds w i t hs te r eocentr e s2or more
enantiom ers
OH
NH 2
OH
NH 2
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s te r eocentr e s2
com pounds
4
OH
NH 2
OH
NH 2
OH
NH 2
OH
NH 2
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s te r eocentr e s3
com pounds
8
HOCHO
OH OH
OH
HOCHO
OH OH
OH
HOCHO
OH OH
OH
HOCHO
OH OH
OH
HOCHO
OH OH
OH
HOCHO
OH OH
OH
HOCHO
OH OH
OH
HOCHO
OH OH
OH
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s te r eocentr e sn
com pounds
2 n
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generalisation !thisis a !
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HO 2 CCO 2 H
OH
OH
HO 2 CCO 2 H
OH
OH
HO 2 C
CO 2 HOH
OH
HO 2 C
CO 2 HOH
OH
s te r eocentr e s2
com pounds
3
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HO 2 CCO 2 H
OH
OH
HO 2 CCO 2 H
OH
OH
HO 2 C
CO 2 H
OH
OH
HO 2 C
CO 2 H
OH
OH
s te r eocentr e s2
com pounds
3 dia ste re ois om ers
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HO 2 CCO 2 H
OH
OH
HO 2 CCO 2 H
OH
OH
HO 2 C
CO 2 HOH
OH
HO 2 C
CO 2 HOH
OH
s te r eocentr e s2
com pounds
3 enantiom ers
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s te r eocentr e s2
com pounds
3 ide nt ic a lm es o
HO 2 CCO 2 H
OH
OH
HO 2 CCO 2 H
OH
OH
HO 2 C
CO 2 HOH
OH
HO 2 C
CO 2 HOH
OH
o
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com poundsm es o
HO 2 C
OH
CO 2 H
HO
HO 2 C CO 2 H
OH
OH
o
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s ym m e try
com poundsm es o
achir a lp lane o f
HO
HO 2 C
OH
CO 2 H
i NH NH
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properties
enantiom er side n t ic a lha ve
NH2NH2
NH2H2N
mp = 41-45Cmp = 40-43C
di t o is om ers NH NH
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propertiesdi f fe re n tha ve
dia s te reo is om ers NH2NH2
mp = 41-45Cbp = 221C
NH2NH2
diff c e betw e e n
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di f fe re nc e be t w e e n
dia s te reo is om e rs
synthesisa s ym m e t ric to
ke y
re
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brittanyculver@ickr
h o w do w e m eas ure
pur ity ?
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NH 2
NH 2
NH 2
H 2 N
NH 2
NH 2
=
80 % 20 % 60 %eeenantiom eric exces s ee
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NH 2
NH 2
NH 2
H 2 N
=
80 % 20 %
4 : 1
e na nt iom e ric rat io (e r)
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NH 2
NH 2
NH 2
NH 2
80 % 20 %
diastereoisomeric excess 60 % dediastereoisomeric ratio 4 : 1 dr
ure
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brittanyculver@ickr
h o w do w e m eas ure
ee?
f righta n d
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ha nde d g lo ve s le f t r ig h ta n d
ide ntic a l
ar e
un tilyou dd h d
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un til you a dd a ha nd
hemis try
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s am et he
David Reeves from Flickr
c h e m i s t r y
dia ste re ois om e rs
n e ed
hemis try
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s am et hec h e m i s t r y
dia ste re ois om e rs
n e ed.
R S
R
R R S R
R S
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OH
Ph CO 2H
DCC,
DMAPOMeF3C i Pr
O H
O
Ph
F3C OMe
i Pr
O H
O
Ph
F3C OMe
c ov a le nt
Mos he r s a c id73J A CS512, 73J OC2143 & 91J A CS4092
de r iv a tis a tion
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HO 2CCO 2H
OTol
OTol
O2CCO 2H
OTol
OTol
S diastereoisomer is insoluble
NaOH
()-propranolol-blocker
OOH
NH
OOH
NH2
OOH
NHionic ( s a lt )de r iv a tis a tion
te m pora ry
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Pere Tubert Juh@ickr
t e m por a r y in te r a c tions
chir a l chrom atography
Si
N H
ONO 2
NO 2
Si
OSi
Si O
O
O
O
OSi
OSi
O
O
O
O
O
Me
Me
silica chiral amine
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as y m m e tr ic
synthesis
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simpologist@ickr
c a na de ns o lide Te tra h de ron, 2 0 0 6 , 6 2 , 9 7 1 3
O
O
O
On -C 4 H 9
H H
s ubs tra te OO
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n -C 4 H 9H
O
OBnOMe
OSiMe 3
n -C 4 H 9
OH
OBn
OMe
O
TiCl 4
77%n -C 4 H 9
OH
OBnOMe
O
100%
0%100% de
s ubs t r a t e c ontr o l
O
O On -C 4 H 9
H H
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SarahWynne@ickr
C
ram
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Cont r o lhe la tionram
n -C 4 H 9
H
BnO O
H
Cl n
Ti
MeO
Me 3 SiO
angleBrghi-Dunitz
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angle
R
R
R
O
R
C OR
R
Nu
C OR
R
NuNu
*
repulsion
Br ghi-Dunitz
C
ram
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LR
O
Z S
M
R
O
Z
M
S L
Nu
LR
Nu OH
Z S
Cont r o lhe la tionram
C
ram
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Cont r o lhe la tionram
L
SZ
LR
O
Z S
M
R
O
Z
M
S L
Nu
LR
Nu OH
Z S
O
R
Z
LS
O
RNu
L
SZ
R
Nu OHZ
LSNu
OH
R
Me
HO
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Ed Bierman@ickr this isnt the right sponge!
pr e s winholide T
e tra h de ron, 1 9 9 5 , 5 1 , 9 4 3 7
OMe
OMe
Me
HO
HOMe
Me
OH OH
Me
MeO
OOHO
s ubs tra te
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OMe
OMe
Me
OSi
OMe
Me
H
O
t -Bu
t -Bu
Me 3 Si Me
TiCl 4
94%95% de
OMe
OMe
Me
OSi
OMe
Me
OH
t -Bu
t -Bu
Me
s ubs t r a t e c ontr o l
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Fe lkin Ahn
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modelFe lkin- A hn
L
M
SH
O
Nu
L
S
M H
O
NuNu
Fe lkin Ahn
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modelFe lkin- A hn
Ph H
O
Me H
Et MgBr
PhEt
Me H
Ph
EtMe H
H OH
HO H
25%
75% ( 50% de )
Fe lkin-Ahn
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modelFe lkin- A hn
Ph H
O
Me H
Ph
HMe
O
H
first ...
Ne wm a n pr o ject iondra w
Fe lkin-Ahn
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modelFe lkin- A hn
Ph
HMe
O
H
H
Ph
Me
O
H
Ph
H
Me
O
H
Ph
Me
H
O
H
p e rp e nd ic u la r
r o ta tela rge group
Fe lkin-Ahn model
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Fe lkin- A hn
Ph
Me
H
O
HEt
Ph
Me
H
OH
Et H
PhMe
H
OHEt
H
PhEt
Me H
HO H
mode
not the w hole
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Ph
O
SMeLiEt 3BH
Phi Pr
SMe
HO H
Phi Pr
SMe
H OH
Zn (BH4)2
t s to r y
che la tion
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i Pr
MeS
H Ph
O
Zn
HH 3 B
a t ionc on tro l
no
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per pendicula r elemen te le c tr one ga tiv e
MeS
i Pr
HPh
O
H BEt 3
ca rbonyl
che la t ion
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Capt Kodak@ickr
sterics electronics
s ubs t r a te
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a t ec on tro l
n -C 4 H 9H
O
OBn
OMe
OSiMe 3
n -C 4 H 9
OH
OBn
OMe
O
TiCl 4