)
Syothesis of Sx Membered Ringsi
a3 gererd eede of mking carko-cyelie 6-membered
vings and tach prodoces rings wik chanocteristie substihation
pathern
The discennechons are aldot (4) and conjugate (Michael)
adt*on (2)- he target mlecde is conjugated cyclchexen on e -
aldol
Michae L
(1) (2) (3) (4)
() Diels Alder
The T.M (5) has-
rup and alkene but non cnly the alkene in the Ring-he
in the -e -grovp
is cutsde the ring and remote from alkene -Ihe simpest ay to do
discoecion by draw the rererse reaciong Sa)
Start
mechanism ct imafno
jour arrowS on akene and whichever way round the
Tig gou prefer- (5aor (sb)
raDiels -
Alder Al der
ci) Reduction of (Sa) (G) () (S6
Aromati compounds
(3 Total (6) Pantal Reduchon , partiudarly
Reduckon
Birch Reduchon
(4) Carbanyl Condensationg:
Robinsor Amelation
Robinson Annelahor is One
importat f al carboryl
otion Leading to Six-memb ered rings
condensotio
Nhen Marx wishe d to Inves tig ate whethe
[Link]
R Jroups
migated bater in rearrangmlui-He wated compomd
be vanied -One of dou ble bond ca be
(4) here R-aroup easily
oxidati on of (2) an idea Robinson Annelaion produt -
put in by 1,3 -Di CO as material ond can be
ec Hon
Disconn reveds that
mode from stmple ester (9 and etnyl famate RcoEt
ConEt
co,et 1,3-oico
FGr CHO 1,5-NCO
Brar CHO (3)
point
RtHCO;Et
(2)
ambiquty n first step of synthcss as only
There bis no more electrophilic- The Robinson annelaton
(4) con enobze and HoEt is used a qnone
stages and fnal oridaton
was cannied out in two
DOQ I5) , a good reagent for dehydroqenaljon -
(DDa)
Na ROt RzNH DDQ
CHO CHO
HOO,Et (koBut) AcOH
o,Et
.1S-dica
Ph Ph
CI)
Ph ph
One extension oP Michael addiHo
is important pathuay to make o6 Membered rings-At frst glance you
-grop
might thiok o Dials Ader dise for i) as it ia cydohesene with
Bu olsconn o «,B double bond reveals a Sirnple L,5-dico
d's -connection -
’ Synthesis - co,Et
Eto
Ph
The Second step of synthass the ydakon effen goes spontaneously
and whole process op addiior ond cyclizatio being a "ig fomaton
or anelahion is Knon as Robinson Annel ation
ntemedi ate in synthes of
F 3, The bicyeli ketone (31) is an tdeal
steroi ds such as (30) as unconjuqated. ketone is correcty placed
to add ying C -The d,B d'sconn on (31) gives 1, S-di ketone (32)
with e xcel ent disconnection at ring cha juncton To ive Symmehie cikaoy.
4 Analysis
1sdico
(30) (31) (32) (33)
’ Synthesis -
koH, MeoH
Sinple cyclohevenoncs can be made by Robinson Annel ation if
necetony after achvalong grap ad diosaj?
Analysis add
Co,Et Co,Et (37)
(35) coEt
(36)
co(oEt)2 HasOy
Eto
co,Et
co,Et
(2) Diels Ader Reaction t
D-A
Uinforturate y,Diels Aler Ron gives orho and para produds
and not mela
products Lke (b) Ths panheulaw reacion
2
[3,31 (Sbuchure 9 sveny clase To tiat
ot Diels Alder dimer q metn
vinyl Ketone and wt ti Rsn
8) Carinspsid) purlbomrget teiratn
’ Analyså 3:
(o) b
(44)
ynthesized?
butadiene complexes.
Q6. Explain bonding in
reduction of metal salt?
metal-alkene complexes
can be synthesized by
Q7. How
carbenes.
Fischers & Schrock
Q8. Differentiate b/w
the basis of
organometallic compounds can be classified on
How
09. What is hapticity?
hapticity?
method for synthesis of tri hepto-allyl complex.
Q10.)Write synthetic
"este
fop ore preswt d Merelotten
ordelect wihlasn
oh cye loje ont
sip lelveen hem eeorized. such a. bans reloliorhip ood
Siglure has just
" he synthelr atracout
fon tron dienoghile (42)
ton be mode -Syothesis
Có,2
(12)
()
’ Analyuis[Limonene]:
D-41
-Sncly
() Reduction of Arornale cormpoundsi
’To tal Reduetion Totel Reduchon of a benzone 1o
Yeques prexure cnd aie catalyst ond ene tasl done
Yg
indushially thonio the lab
Synthesi Anispasmdiu dnug (oiyelomine)cauni be rnade by
This syplbes illushles hot 06-rembered rinqs eseiPeN
melhols olev lhan melhocds presented Nuonnection
with one ring tht could be arornatto (22)
add (21) th
C-0
Oster
CooH
S o N E t ,
(21) Ph^cN
Synthetis
Na H
Ph^CN NaNila,NHs
EtDH
co,tt
H
FGA
yldion tt-BuCI
Syrthesis
OH CyOs
H2,N
oY tBucl ,AIO,
’ Analysis i
NH
FHA C-N
EtO OEt
Eto OEt
’ Synthesis NHL
Base
OH EtBY 12)
OEt OEt
’ Birch Reductioni
aie Compounds by
Brch Roduclien is parlial Redocion ot oom
lecton - trons fer from d'ssoling metal usualy Na in liq NH3 ,ov Li
thylomine in pressence of veak elactuon donor to qiut Alcohol:
Tne rn behaves as if were an ntemediate qives non
dianion
onjugated dienes- The tDG subs gives producks (33) and repels Quins
(32)
While ENG atacts Cunions » prduct (35)
54)
i) t-BuOH
(30) H
CooR
R-OH,
ome Ome
(32) OMe (33)
d, Araly
1,2 -dico Birch
Redn
’ Synthesis i Na Poph thalke
me oH, NH3 Aid
product in bok ik [Link] tenains
on doutle b d
ohen Pangelt for Poahol Peddhor o ormohi
rony be corbalod by
e4 for Pedu hon of Nopbolene ton
tphan
H
Preparatior of 1,6-bifuncbenalzed Coropounds t
Reconntction is the vgual shcteqy fe tomthatcing !t-b kotzed
Compourds
4conpcund Sree cyeleicret vequircdfou oxaakie
cxdalive eleavege are
easily made-Atipt aid (1) au lable from cvycdoheneme thef and o
Source o 5-menbened rings by cantenom rns
(Adipic aid)
coOH
Cyclohexena wih Subs in -paikon, made from celoheranore
cylexaroe anda
oyketo- aldehyde
gie ketbR aids, or
Ghigand re agens leove to five
OH
H
^cooH
Anal,sis i reConnect
&-B tr CHO
’ Synthesis 3
Me
CHO
ort -CHO
H*
H
-ZH
a
t
Diels Alder Route tomake1,6-biCO 1
t The lost example ? clear thad ve nonally have to make
and one ot bert route is
Cycche nene Ne need for onidlive -cleavage
eest
els Adey KeachonE3ysa pd ittio
coOH Tho prdut have 1,8
H,0a
CooH rcatinship blw two
pla
adds
ha
ome recomect
siz Meooc oR F61
Me 00C vme Redn
pla
ow
O-A
iffe
ha
Redn Mer oMe
Ome
ome CH2
CH
ZntH,0 or aome cooHome
NiH Coome
CooMa
H
ofMe
ome
4 The
The bicyelie double lactoe is used as precorsor for all foor helo
ycie tin8 inin their synthesi of Vilain B,- Disconnec Hion of Bot
laclones yields kelone. 6
-cool
’ Analysis-cOOH CoOH
oon H CooH
2C-0, cooR rOomect
este
D-A CoOH
Aldol COOH
CoOH
OR
CooH
coOH
çooH CooH CoOH,
+ HsPO SnCly , H
CO3
CHO 86° (ynr2r
Coo
OH cooH
Coow
OH ol
Oidative cleavag by Bacyer - Vilagu Oidohen i
Cydohesanones nay also be cleaved oidatively to perauds
Yearrangnent nhich has efec of insenting Uen atom into ring to
give lactone
tR-ç-0-otH
-RCOo
+ RcOOH.
Anayai
CooMe
’ Synthesis - oMe
OMe
MeoH,
G [T4]
’Baeyer - V: Mager Oridaon ia regioelechiye , he
is rmore
Subst group migrotes ond steneopecfe , it dses so with rebsnken
Anolysi Oct n econnect FGI Pedn
oH (onid)
’
Syothesis
H2 sepor ate Cros
rnCPBA
Ni P+ (Tores
OH ot <oH
Paog)
ot-n. -0ctL:
Analysis
C-c Br
1,3-dico
cooEt LeooEt
B
HBr
()
EtoH cooEt
ccott
Conc HCI
coOE o Eto cuoEt
coEt