5K AJ - 5 2+

#

+DE EA HC= EGKA

2=HJEA 11  5O JD IA IJ H ? @A =   EHE@ OH ?E A
+ A J=EHAI

JH

2H > A @A @E ?K J OA A ANF EJ=> A F=H H?A=KN > A KJE EI=JE @A = 4 A F=HJE?K EAH 2=I @A GKAIJE I L= HEI= J = FH=JEGKA ANF HE A J= A 4 @=?JE I KLA J =FFH NE =JELA =EI = LK FEHA GKA GKAI GKAIJE I @ >E AI B H K A @A AMEI @K @E NOC A I= I ? A J=EHAI A JHA =KJHAI AJ @AKN CH IIE HAI AHHAKHI @= I A ?O? A ?= EIJEGKA @A = H =?JE H=@E?= =EHA 3KA GKAI GKAIJE I @E ?E AI F KH GKA GKK GKE = F=I @ F=II A FH CH= A =JE IJ H ?DE EA @A = ?O? EI=JE  A ?DEAH JAN AIJ @= I A @ IIEAH EFF - 52+# EF 7 ? FE ? AH @K JANJA AIJ F IIE> A LAHI M H@ =FH I E E =JE @AI I? HEAI @A ? @A =6A: AI CKHAI I J =K B H =J AFI K =K B H =J  @E => A HJ@ B H =J @A ?DEAH @A MEJ= "  FH CH= A CH=JKEJ @EIF E> A IKH A IEJA @A *E H=@ = = @A ? KHHEA = = @A( H@ AJ BH

 5O JD IA @K FH ?KHIAKH
 A  = EJ F II @A " ?A JHAI =IO JHEGKAI E @EGK I IKH = CKHA 
OH HO
R R R

OH
R

OH

OH

OH

.EC   5JHK?JKHA @K

EJ @A K A JA F H=JKHA AJ K I L= J

 @

A FH NA   E @EGKA GKA A ? I AIJ @ANJH COHA

F I F KH K A

CKAKH @

  ! 1 AIJ = FHE HE E F IIE> A @A ? J KH AH A

F ?DEH=  F KH FH F=HAH @AI FH @KEJI ? F ANAI ,A = E HA  >JA EH GKA A IAK IJ H EI HA E J HAII= J E ? LEA J @A AJJHA A KLHA @AI JH= IB H =JE I = JE AJ @E=IJ H I A?JELAI +A AI ?E ?AIIEJA J K A J K K =KJHA @KJE EIAH K =KNE E=EHA ?DEH= H =?JEB K ?=J= OIAKH AJ = FH F=H=JE @A ?A KE ?E E F EGKA K A J=FA K K A =KJHA @A = IO JD IA @KJE EIAH K FH @KEJ ?DEH= I KLA J =JKHA 1 ANEIJA @A JH I H=HAI ?=I @A
@ @ K> A A J IF J=  K = JE HA ?HEIJ= EIA @= I K A IJHK?JKHA JHE@E A IE A A A A =KIIE ?DEH= A = HI GKA =KJHA ?HEIJ= EIA @= I A A JOFA @A IJHK?JKHA ,= I ?A ?=I FAKJ AIF HAH ?A BKJ = ?D= ?A @A 2=IJAKH =LA? AI J=HJH=JAI @A F J=IIEK AJ @= EK  I F=HAH AI @AKN = JE HAI I= I E JAHLA JE @A J KJ =KNE E=EHA ?DEH= ?AIJ = IJHK?JKHA !, GKE A KA A H A ,= I = = HEJ @AI ?=I J= J = H I KJE @K = CA H=? EGKA GKA  => H=JE = JE I A?JELA AJ @E=IJ H I A?JELA @K IJ H EI HA HA?DAH?D HAGKE HA J KI=CA @K ?=J= OIAKH K @K H =?JEB ?DEH= =JKHA K IO JD JEGKA

5K AJ - 5 2+

#

+DE EA HC= EGKA

  A ?D HKHA @A E ? AIJ K =?E@A @A AMEI GKE KA A A H A GKA =?E@A @A *H IJA@ KIKA A A J E JH @KEJ F KH ?=J= OIAH K A =? J= EI=JE 1 = F KH >KJ  @AN= JAH  A?JH FDE EA @K CH KFA ?=H> O A @A =? J A  @= E HAH =FJEJK@A K? BKCA @K CH KFA DO@H NO A @= I AI E JAH @E=EHAI H =?JE AI  A ?= EI A @A B H =JE @K ?O? A =? J= EGKA AIJ ? =IIEGKA 1 AIJ HAFH @KEJ IKH = CKHA 1 B=EJ E JAHLA EH AI J=FAI IKEL= JAI  =@@EJE @K ?D HKHA @A E ? IKH A CH KFA ?=H> O A A LKA @A AN= JAH  A?JH FDE EA =LA? @ F=HJ @K E ?D HKHA  =@@EJE K? FDE A @K = EJ IKH =? J A ? F AN A F=H E JAH @E=EHA @K CH KFA DO @H NO A A F KI @ C=C  A F KI K? FDE A = FHE HE   ?D= CA @A IEJA F KH K E DO@H C A = @= E HAH =FJEJK@A K? BKCA @K CH KFA DO @H NO A  @ F=HJ @A
0+  AJ B H =JE @K ?=JE @A JOFA F KI N EK GKA ?=H> EK IJ=>E EI F=H @ ?= EI=JE A?JH EGKA  KLA A =@@EJE K? FDE A F KH @ AH A ?O? A # ?D= I IKELEA @A = B H =JE @A ?D HKHA @DO@H C A KE A ?=J= OIAKH @A = JH= IB H =JE AJ @A =? J= @ IEH
ZnCl2 ZnCl ZnCl AdN2 O
activation

ZnCl2

Cl

ZnCl OH

OH

OH

prototropie

O O

O O O H O AdN2

OH "ZnClOH"

ZnCl OH

O OH

.EC

?= EI A @A =? J= EI=JE

 ! 1 FAKJ IA B H AH @AI ?O? AI @E NOC I # $ K % ?D= I ANF HEA ?A JHA GKA A ? F I = HEJ=EHA AIJ A ?O? A FA J==J EGKA 1 FAKJ =KIIE IA B H AH K A ?K A F II @= J ! ?O? AI FA J=L= A JI K K IAK IA A >HA @A CH KFAI 0 E F EGK I @= I = JH= IB H =JE  " A >KJ @A = JH= IB H =JE @E NOC AIJ = FH JA?JE @AI @AKN CH KFAI 0 A C=C I @= I A ?O? A

 !  ,= I A J JH==? J=JA @A F > 2>( )?)" A @ACH @ NO@=JE @K F > AJ C= 18 ,= I A FH @KEJ = 2>( )?) E AIJ C= 11 1 O = @ ? AK H @K?JE @K F > AJ ? KFKHA NO@= JA @K @E ! A ? F I AIJ HAFH IA J ?E =FH I CKHA ! A @AI?HEFJAKH IJ H ?DE EGKA @A =J A @A

5K AJ - 5 2+

#

+DE EA HC= EGKA

?=H> A =IO JHEGKA AIJ @ @A ?=H> A =IO JHEGKA AIJ

IKH = CKHA E AIJ C= > + > !+ > 0

4

 H@HA @A FHE HEJ =KJ KH @A =J

OH O O OH

O O

Pb(OAc)4 Pb(OAc)2
S

O O O compos 2 H

compos 1

.EC !  5JHK?JKHA @K ?

F I

 "  AI ! ?

F I I != !> AJ !? I

J @E=IJ H EI

HAI A @A IE E?A K @= K E A HA

 " 1 AIJ @ ? A LEI=CA=> A @A AI I F=HAH F=H ?DH =J CH=FDEA IKH ? ? =IIEGKA A =>IA ?A @= KL= J ?DEH= CHA IKH = FD=IA IJ=JE =EHA  #  AI IJHK?JKHAI @AI ? A @E AJ = FH F= A F I I " AJ # I J E @EGK I IKH = CKHA "

DO@H OIA @A =? J= H C

CH3

O O

CH3

O O

CH3

OH OH

OH

Ph Si Ph

OTBDPS

compos 3a

compos 4

compos 5

.EC "  5JHK?JKHA @AI ?

F I I " AJ #

 # 1 I=CEJ @K A JD HE ?=JE IE?  F KI FH ?EI A J @K A H =?JE @A JOFA 9E E= I A >E = AIJ ?A KE @K A IK>IJEJKJE K? FDE A =EI = =JKHA @K ?= EI A AIJ F=I E @E=JA 7 A S 2 = J KJAI AI ?D= ?AI @ JHA AN? KA ? FJA JA K @A A ? >HA A J =KJ KH @A =J A @A IE E?EK 7 ?= EI A @A JOFA S 1 AIJ J KJ B=EJ A LEI=CA=> A ? @EJE GKK E IE O EK JAHJE=EHA I EJ =KIIE IJ=> A GKK E ?=H> EK = = CKA =EI K ?= EI A @=@@EJE IKELEA @ E E =JE AIJ =KIIE FH >=> A ? FJA JA K @A = ?=F=?EJ @K IE E?EK =??AFJAH F KI @A " @ K> AJI @ A?JH I @A L= A ?A  # ! E E@= A AIJ K A >=IA GKE FAH AJ = @ FH J =JE @A E JAH @E=EHA H =?JE A 1 AIJ FAK LH=EIA > => A GKA E E@= A FKEIIA @ FH J AH = ?  A FK) @K ? KF A 1 0 /1 AIJ L EIE @A % @= I A=K A F=II=CA =K , . A @ EJ F=I FAH AJJHA K A =KC A J=JE IK I= JA @A I= L= AKH  # " 1 IA FH @KEJ K DO@H C A A I KJE ?D= CA FH J JH FEA A JHA AI @AKN IEJAI = J I F=H E JAH =GKAKIA A I?D = @A = CKHA # A AIJ K A @ EI=JE @E=EHA @AI E=EI I IE F E A IAK AI

5K AJ - 5 2+

#

+DE EA HC= EGKA

"

doublet engag dans la liaison H N H O H H O H O H H O H H O O H O H H H N H H H O H N N

doublet engag dans la liaison H O H H H O H

H H

.EC #  2H J JH FEA @= I E E@=

GKA GKAI E=EI I DO@H C A J J HAFH IA J AI = JH= IB H =JE E F EGKA =KIIE K A H HC= EI=JE A?JH EGKA =K IAE @K ?O? A +A A ?E A F IA =K?K FH > A AJ E B=KJ @=E AKHI JAH GKA E E@= A AIJ K ? F I =H =JEGKA J KJ ? A I =?E@A ? KCK *EA HA =HGKAH GKA AI E=EI I DO@H C A @ALEA A J @AI E=EI I ? L= A JAI AJ LE?A LAHI= FA @= J = FH J JH FEA FD A GKE A @A = @A GKA JH I FAK @ AHCEA AJ A @E A F=I A JH FEA @K IOIJ A @A = E HA IA IE> A  # # =?E@A JHE K H =? JEGKA ?=J= OIA DO@H OIA @A =? J= ? GKAIJE I   AJ  A E ?=J= OIA I= B H =JE 8 EH

 # $ +AJJA GKAIJE A @ALH=EJ F KI CKHAH @= I K FH > A @A ?A ELA=K I=EJ @AFKEI F KI @A ! = I GKA = ? HH =JE A JHA IJHK?JKHA AJ =?E@EJ AIJ JH I @ E?=JA AJ GKA AI ANF E?=JE I IJHK?JKH= AI I J E A A J B=KIIAI 5AK A K A = = OIA @AI JAH AI A JH FEGKAI   JK@A AIJ ? =IIEGKA @= I A ?=I @AI =?E@AI ?D H =? JEGKAI AJ AI L= AKHI I J @EIF E> AI FAH AJ @A HA @HA ? FJA ? HHA?JA A J @A =KC A J=JE @K FK) @AI ? KF AI GK= @ A >HA @=J AI @A ?D HA =KC A JA @= I = ?K A - A AJ =?E@EJ A I KJE =GKAKIA AIJ AIIA JEA A A J E A =KN FD AI @A I L=J=JE @E HA JEA A ,= I A ?=I @A =?E@A JHE K H =? JEGKA AJ @A =?E@A =? JEGKA AI @ AI JDAH @O = EGKAI I J AI IKEL= JAI H B HA ?A 0 =I E 6DA FDOIE?= >=IEI B HC= E? +DA EIJHO NB H@ I?EA ?A FK> E?=JE I @ AI T = 298  , FK) A
1 1

0! ++

0/0! ++ " %$ % 

.! ++

0/.! ++  ! !  !

H G / H H /

T H S /

%!

= LKA @A ?AI @ AI E AIJ ? =EH GKA ?A AIJ F=I A JAH A IJHK?JKH= E A JD= FEA IJ= @=H@ GKE AIJ HAIF I=> A @A = @E HA ?A @=?E@EJ A JHA AI @AKN ? KF AI - HAL= ?DA  L KJE @AI JAH AI A JH FEGKAI AIJ F=HB=EJA A J ? HH A =LA? ?A A @AI FK) @AI ? KF AI AI JAH AI A JH FEGKAI I J C=JEBI ?A GKE E @EGKA K A F KI CH= @A IJHK?JKH=JE @K E EAK ? JA = J AI E I GKA @= I A ?=I

5K AJ - 5 2+

#

+DE EA HC= EGKA

@AI ?K AI 1 IA > A GKA E =? J=JA I EJ >A=K? KF EAKN I L=J GKA =?E@A =? JEGKA  = ?D=HCA C=JELA AIJ ?= EI A IKH K A ANJH EJ @A E  = HI GKA E JHE K H =? J=JA AIJ I L=J @A = E HA = = CKA =?E@A JHE K H =? JEGKA +A FD A FAKJ JHA E JAHFH J F=H A B=EJ GKA A CH KFA JHE K H JDO A JH I B HJA A J A?JH =JJH=?JAKH =JJEHA KE AI A?JH I @K CH KFA ?=H> NO =JA AJ @A ?A B=EJ E EJA = H HC= EI=JE @K I L= J HI @K F=II=CA @K A ?K A @=?E@A E = H F=HJEJE A?JH EGKA J= J @ B HJA A J @EIIO JHEGKA @= I = ?K A
JA

E AIJ ? =EH GKK A JA A H F

IA A FAKJ JHA >JA KA @A = F=HJ @K

LA @A 2+

 $  = H @K?JE @K CH KFA ?=H> O A = FHE HE @ A K =? ?A GKE AIJ ? H F=H = 1 FH IA ?A @AI >= @AI =HCAI LAHI 3 450 ? A IEC = @K O=K @A =J A @DO@H C A @K CH KFA 0 @EIF=H= J HI @A =@@EJE @A=K KH@A F=H IKEJA @K ?D= CA EI J FEGKA A JHA 4 0 AJ ,  E IA B H A 4 , AJ , 0  E AIJ @ ? B=?E A E@A JE AH ,= I A ?=I @K ? F I %= E I=CEJ @K JHEF AJ @ ? A CH KFA 0 AIJ F HJ F=H K =J A @A ?=H> A FHE =EHA CH KFA +0 0 AI =KJHAI IEC =KN I=?? H@A J >EA =LA? A FH @KEJ @A H @K?JE
H = A @A = @ DO@A $  AI IEC =KN = 7, 70 AJ 7, 40 FF I J ?=H=?J HEIJEGKAI @A O=KN @=J AI @DO@H C A @A CH KFAI FD O A IK>IJEJK I =FF=HJA = J =K CH KFA 6*,25 HAIFA?JELA A J 0 A J= E J CH=JE " AJ 0 A HJD AJ F=H= E J CH=JE $  A IEC = = 1, 10 FF AIJ =JJHE>K =KN ' O=KN @AI =J AI @DO@H C A @K CH KFA JAHJ >KJO A @A ?A A CH KFA 6*25 1 I I J J KI GKEL= A JI AJ =K?K ? KF =CA A FAKJ JHA LK A JHA ?AI O=KN F=H IKEJA @A AKH EI ?DH EA AJ AKH EI C= EA  A @ K> AJ = 1, 04 FF AIJ =JJHE>K =KN ! O=KN @AI =J AI @DO@H C A @K CH KFA JDO A 3 A E JAH=?JE =LA? K IAK O=K  ?A KE @A 0 !+  F=H K A ? IJ= JA @A ? KF =CA J = 6, 7 0  ? FJA JA K @A = L= AKH @K @ F =?A A J ?DE EGKA AI @AKN IEC =KN LAHI = 5 FF I J =JJHE>K I =KN ! O=KN @AI =J AI @DO@H C A LE O EGKAI F HJ I F=H = @ K> A E=EI 1 AIJ F IIE> A @A H= AH = = OIA A ? =EII= J K H@HA @A CH= @AKH @AI L= AKHI @AI ? IJ= JAI @A ? KF =CA A A AJ K A ? IJ= JA 3 J = 17, 3 0 E @EGKA K ? KF =CA @A JOFA JH= I GKE FAH AJ LH=EIA > => A A J @A F IEJE AH ?A O=K =K FEA@ @A =J A "+ A K JEF AJ = 5, 44 FF AIJ = HI =JJHE>K =KN @AKN O=KN @AI =J AI @DO@H C A 0 #+ @K CH KFA JDO A JAH E =  ? FJA JA K @A = L= AKH @K @ F =?A A J ?DE EGKA AJ @A = KHA @K =IIEB A IEC = = 3, 73 FF AIJ =JJHE>K =K O=K @A =J A @DO@H C A 0  + E AIJ ? KF =K O=K @=J A @DO@H C A 0 !+ ?A GKE @ A K @ K> AJ @ J ?D=GKA H=EA AIJ ? =J A A JHEF AJ F=H A ? KF =CA =LA? AI @AKN O=KN @AI =J AI @DO@H C A 0 +  A K JEF AJ = 3, 50 FF AIJ =JJHE>K =KN O=KN @AI =J AI @DO@H C A 0 + @=FH I = L= AKH @K @ F =?A A J ?DE EGKA AJ = K JEF E?EJ  A A IEC = = 2, 38 FF AIJ =JJHE>K =K O=K @A =J A @DO@H C A 0 !+ = CKHA $ @ A = IJHK?JKHA @K ? F I %= = IJHK?JKHA @K ? F I %> AIJ E IE @E=JA = B H A @K IEC = @K O=K @=J A @DO@H C A @K CH KFA 0 IEJK = 2, 45 FF =EIIA FA IAH GKA ?A ? F I AIJ K = ? IA? @=EHA  A O=K A GKAIJE AIJ ? KF LEIE> A A J K IAK O=K @DO@H C A AI IEC =KN ?=H=?J HEIJEGKAI @AI O=KN @=J AI @DO@H C A @K CH KFAI 6*,25 ?AKN F HJ I F=H = @ K> A E=EI AJ ?AKN @K CH KFA JDO A I J HAJH KL I HAIFA?JELA A J  = 7, 68 AJ 7, 41 FF F KH AI O=KN 0 @AI CH KFAI FD O A  = 1, 08 FF F KH AI O=KN 0 @K CH KFA JAHJ >KJO A  = 5, 84 AJ 5, 05 FF F KH AI O=KN 0
LE O EGKAI  = 1, 00 FF F KH AI O=KN 0 @K CH KFA JDO A +A?E =EIIA FA IAH GKA = IJHK?JKHA @A = ?D= A ?=H> A = F=I J @E A

5K AJ - 5 2+

#

+DE EA HC= EGKA

= 1,04 ppm

= 2,38 ppm = 3,50 ppm

= 5,44 ppm

H
5

H3C 6 H
4 3 2

H
1

H O = 1,48 ppm

H = 5,79 ppm

OTBDPS = 3,73 ppm

.EC $  5JHK?JKHA @K ?

F I %=

A IEC = = 2, 35 FF AIJ LH=EIA > => A A J =JJHE>K =K O=K @A =J A @DO@H C A 0 !+ ? A @= I A ? F I FH ? @A J = IAK A I KJE H=EI => A F KH GKA A ? F I %> I EJ K =? IA? @=EHA AIJ @E =CE AH GKA A CH KFA 6*25 = ECH @A I= F IEJE E EJE= A LAHI A CH KFA 0 FHE =EHA EIIK @A = H @K?JE @K CH KFA ?=H> O A @A = @ DO@A ) HI E O = ? D HA ?A =LA? AI @ AI AJ E AIJ F IIE> A @=?DALAH =JJHE>KJE A K JEF AJ = 3, 65 FF AIJ = IKFAHF IEJE @AI IEC =KN @ I F=H AI O=KN @=J AI @DO@H C A @K CH KFA JDO A JAH E = AJ ?A KE @K CH KFA +0 0 =@ =?A J CKHA %
= 1,00 ppm = 2,35 ppm = 3,65 ppm = 5,05 ppm
a

H
5

H3C 6 H
4 3 2

H
1

OTBDPS

= 2,45 ppm

H = 5,84 ppm

O H

= 3,65 ppm

.EC %  5JHK?JKHA @K ?

F I %> F I 2

 $  + FJA JA K @A ?A GKE FH ? @A AJ IKEJ  FAKJ H=EI => A A J FA IAH GKA A ? H IK JA @A = ECH=JE @K CH KFA 6*25 IKH A CH KFA 0 A F IEJE + CKHA &

$ A ? F I  A H =CEJ F=I ?=H E O = F=I @A

HA =EI @A CH KFA 0 IKH =J A @A ?=H> A =@ =?A J F KH FAH AJJHA A JH= IBAHJ @K CH KFA 6*,25 J I GKA @= I AI ? @EJE I ?D EIEAI F=I @=?E@A A CH KFA FH JA?JAKH A FAKJ JHA = A?J AJ A @E JAH E = HAIJA =IGK $ !+ A KI =L I @ E @EGK A IE E?EK A J @A = JH EIE A F HE @A FAKJ =??AFJAH @= I I= ? K?DA A?JH EGKA @A L= A ?A F KI @A " @ K> AJI 1 AIJ @ ? F IIE> A @A FH F IAH CKHA ' K

5K AJ - 5 2+

#

+DE EA HC= EGKA

CH3 O O

OH OH O

CH3

OTBDPS OH O

CH3

OH OTBDPS

OTBDPS compos 8

OH compos P

OH compos 9

.EC &  5JHK?JKHA @K ?

F I 2

?= EI A = ECH=JE @K CH KFA 6*,25 B=EI= J E JAHLA EH LH=EIA > => A A J = @ FH J =JE FH = => A @K CH KFA 0 E>HA = B H =JE @A E JAH @E=EHA FA J=L= A J +A KE ?E I KLHA F KH HA@ AH A ? F I @A @ F=HJ K A FH @KEJ 2 @ FH J I AJ K JH= IBAHJ @E I DO@H C A FAH AJ = B H =JE @A 2 FKEI = B H =JE @A ' F=H K ?= EI A = = CKA
HO OH OH O Si Ph t-Bu Ph O

CO32 HCO3
O Si Ph t-Bu Ph

qu.

OH conform. O Si

O Ph Ph t-Bu HO

compos 8
O HO OTBDPS OH O OH OH Si Ph
qu. conform.

HO

Ph

Si Ph t-Bu

HCO3 CO32
O O Si Ph t-Bu Ph

compos P

Ph t-Bu

.EC ' 

?= EI A @A B H =JE

@K ?

F I 2

 $ " = H @K?JE F=H E) 0" ? @KEJ K J JH== ? NO= K E =JA @ J A JH=EJA A J F=H DO@H OIA LH=EIA > => A A J =?E@A FAH AJ = B H =JE @A = ? =K?K A J E O = AK B H =JE ?AII=EHA F KH = ECH=JE @K CH KFA K F IIE>E EJ @A B H =JE @A = B H A @ FH J A @A %= 6*,25 - HAL= ?DA HI @A = H @K?JE F=H =*0" A FH IA ?A @A JD= E IA B H A @EHA?JA A J %= AN? I @DO@HKHA J K KHI FH IA J AJ GKE F II @A @AI FH FHE J I >=IEGKAI  FAKJ FAH AJJHA = ? = @ FH J =JE @A ?A @AH EAH AJ F=H IKEJA = ECH=JE @K CH KFA 6*,25 KI F KL I FH F IAH A ?= EI A FH F I CKHA  L= E@ F=H @AI JK@AI A 4 @K O=K @A > HA F KH = H @K?JE @K ?=H> O A F=H =*0" A FH IA ?A @A JD=  K @ JD= A A @A HAB=EHA A @AIIE  =?JA AIJ GKA FIAK@ JHE ?K =EHA ?=H A JD= AJ A ? F I ?=H> O I J FH =II ?E I F=H = IA FEJAH A A E=EI DO@H C A GKA BAH=EJ I= I A A  =KJ KH @K ?=JE I @EK HAFH IA J  $ !  AI ? F I I  = AJ  > I J @AI EI HAI @A F IEJE

5K AJ - 5 2+

#

+DE EA HC= EGKA

&

O O H H B H H O Et O H H H B

Et OH + EtOBH3 H

tat de transition cyclique, 6 centres, en conformation de type chaise

.EC   4 @K?JE

@K CH KFA ?=H>

O A F=H E

> H DO@HKHA

 $ ! 8H=EIA > => A A J = JH= IB H =JE * AIJ I KI ? JH A JDAH @O = EGKA  A JA FI @A ? J=?J AIJ F KI C AJ = >=IA F KI B HJA FAH AJJ= J A JH= IBAHJ @A CH KFA 6*,25 ?A GKE B=EJ GKA = JH= IB H =JE ) AIJ I KI ? JH A ?E JEGKA =E JA = J L= I=L EH F KHGK E  %   GK=JE @A = H =?JE @A @ FH JA?JE

F + %a = HO + 3
= K A A JD= FEA IJ= @=H@ B HJA A J C=JELA @K B=EJ @A = JH I CH= @A A JD= FEA IJ= @=H@ @A @EII ?E=JE @A = E=EI 5E. ? F=H A ?A A @A = E=EI 5E ,K B=EJ GKA = I A = C >HEGKA @AI >HAI IJ ?DE JHEGKAI @AI I KJ I AIJ K A A JAH A A JH FEGKA @ EJ JHA @A B=E> A L= AKH =>I KA AJ =E IE A JD= FEA E>HA IJ= @=H@ =JJ=?D A  GK=JE @A @ FH JA?JE @ EJ JHA B HJA A J C=JELA ?A GKE =IIKHA A C H= K A JH= IB H =JE J J= A % AI @AI?HEFJAKHI @AI @AKN =J AIJ  5 !5  ! JDO FA J " A  AI @A ?=H> @E A =IO JHEGKAI I J5 A IOIJ =JEGKA @A !

5O JD IA @A EHE@
  AI B H K AI @A AMEI @A  F=H F KIEAKHI B H K AI I HAI @ @ NOC A JAH E =

OH

?E A
 A AIJ HAFH IA J A A?JH FDE A IKH =J A

AI J@ AI IKH = CKHA IKEL= JA J K A GKE B=EJ =FF=H= JHA K ?=H=?J HA

O O O O O

O O O

.EC   5JHK?JKHA

A?JH

EGKA @A 

A A HAFH IA JA F=I = B H K A @A AMEI @K @E NOC AMEI A FAKJ HAFH IA JAH ?AJJA ?K A  

A ?=H ?D=?K I=EJ GK=K?K A B H K A @A

HI @A  =JE E IA B H A @= I K FHA EAH JA FI K E@A CKHA  F=H =@@EJE @A  A IKH = @ K> A E=EI IA K A H =?JE @A ?O? =@@EJE  ?= EI A A?JH ?O? EGKA =KJ HEI F=H IO JHEA @K B=EJ @K HA? KLHA A J @AI H>EJ= AI BH JE HAI +A ? F I L KA F=H K A H =?JE

5K AJ - 5 2+

#

+DE EA HC= EGKA

'

cycloaddition

O O O

cyclorversion

O +

O O

cycloaddition

O O O ozonide

O O O molozonide

.EC  

?= EI A I?D

=JEGKA @A 

=JE

@A ?O? H LAHIE A K ? F I ?=H> O AJ K E JAH @E=EHA E IJ=> A 7 A KLA A ?O? =@@EJE =KJ HEI A F=H = IO JHEA @AI H>EJ= AI BH JE HAI FAH AJ = B H =JE @A  E@A

 4A =HGKA I= I K A ? =EII= ?A D HI FH CH= A  @K ?= EI A ? =IIEGKA @A +HEACAA E AIJ @E ?E A @A H F @HA ?AJJA GKAIJE  5A F IA @=E AKHI = GKAIJE @AFKEI GKA GKAI = AI @K A FHA E HA J=FA @A JH= IBAHJ A?JH EGKA A JHA  A AJ = ? A
JA  ? F=H A @A JH=EJA A J F=H A JD= AJ IKH A I?D = E AIJ B=EJ A JE @A A=K DO@H OIA @A  E@A @ A >EA AI FH @KEJI = ? I =EI = JD= OIA @ A F KJ J K FAH NO@A =? J= EGKA K CH KFA A HA F =?A A CH KFA 0 @= I D E=? J= 

 ! = ? H=JE > AKA H IK JA @A = FH IA ?A @ A @= FAH AJ @A @ JA?JAH = @A  NO@=JE @A = ? A 1 B=KJ ? JE KAH A F=II=CA @K KN @A C= ?DE EGKA @A A J =HH JAH  EIAKH  F KH L=?KAH AN? I @ A ? ?A JH A @E @KHA @A F J=IIEK AI E I E @KHA I J AN? I

I A

E EAK H =?JE

A 5

=FF=HEJE

A J E AHJA ?AIJ F KHGK E E B=KJ LE LAHI K FE CA A C H= K A I KJE NO@ I A E I JHEE @KHA F=H  A A

 " 2 KH GKK ? F I IAHLA @E @E?=JAKH @A @ OIA E B=KJ GKE FKEIIA JHA NO@ F=H  A E I B=?E A A J GKA = ? A @K F E J @A LKA JDAH @O = EGKA IE E A IAHJ HEA  AJ GKA = B H A NO@ A AJ = B H A E EJE= A H @KEJA ? B HA J = I KJE @AI ? K AKHI @E HA JAI - C H= E @E?=JAKH AIJ K A AIF ?A F II @= J @AI A?JH I @ ?= EI I = @=>I H>AH @= I A LEIE> A AJ @A ? B HAH = I KJE = ? K AKH ? F A J=EHA @A ?A A @A = H=@E=JE =>I H> A A 5K@= 4A@ F II @A ?AI FH FHE J I 1 @ EJ =KIIE JHA NO@=> A ?AIJ A ?=I @K FD K @K IOIJ A @E= GKA A A L EI F=I ?A GKA  FAKJ = KJAH @A IE F A # A IOIJ =JEGKA @A 22D! AIJ =E JA = J A JHEFD O FD IFD= A 1 AIJ NO@ A NO@A @A JHEFD O FD IFD= A 22D! F=H  E@A K K BH=C A J FAH N @A ?A KE ?E  A @ J=E @K ?= EI A AIJ F=I =IIKH  A ? F I # AIJ K = @ DO@A ? FJA JA K @K JH=EJA A J H @K?JAKH GK= IK>E  E@A ?A GKE @=E AKHI = HEA @ LE@A J GK= @ A? = J F=I AI FH FHE J I ?DE EGKAI @K JHEFD O FD I FD= A  AJ IKHJ KJ I=?D= J GKA = JH= IB H =JE GKE IKEJ AIJ K A H =?JE @A 9EJJEC 5= IJHK?JKHA AIJ FH IA J A IKH = CKHA ! - ?A GKE ? ?AH A AI @ACH I @ NO@=JE @K FD IFD HA @= I AI @AKN ? F I I = H F IA AIJ @ E?=JA 1 AIJ @E ?E A @A @ EH @AI @ACH I @ NO@=JE A ?DE EA HC= EGKA ? A ?D=?K I=EJ 6 KJ ?A GKE AIJ ?AHJ=E AIJ GKA A @ACH @ NO@=JE @K FD IFD HA = =KC A J @= I = JH= IB H =JE @A @AKN K EJ I LH=EIA > => A A J $ A ? F I $ H IK JA @K A H =?JE @A 9EJJEC 5= IJHK?JKHA AIJ FH IA J A CKHA " AI

5K AJ - 5 2+

#

+DE EA HC= EGKA



CH3 1) O3 O O compos 14 2) PPh3 H O

CH3 O O + H

O H + O

Ph P Ph Ph

compos 15

mthanal

oxyde de triphnyphosphane

.EC !  *E =

@A 

OIA =

=JJHE>KJE

I @AI IEC =KN @A 4

J E @EGK AI IKH A I?D

 4A =HGKA K A J=> A @A L= AKHI @A ? IJ= JAI @A ? KF =CA A J J = >EA LA KA = @A ? H AH A ?=H=?J HA -  @A = @ K> A E=EI +A KE ?E AIJ =IIKH F=H = L= AKH AL A @A 3 = ? IJ= JA @A ? KF =CA JH(2 C)H(3 C) - KJHA AI O KHAI IJ=>E EI I ? A ?A KE KJE EI I J H FKJ I F KH @ AH K = ? A -  =LA? K A JH I > A @E=IJ H I A?JELEJ
= 1,06 ppm CH3 O O H + Ph Ph P Ph COOEt H = 4,20 ppm
H H O H H O

= 1,31 ppm O
8

= 5,78 ppm
H H3 C O
2 1 3 4 9

= 2,50 ppm = 4,02 ppm

H H H H3 C

OPPh3

11

CH3

= 6,97 ppm = 3,64 ppm

10 CH3

= 1,42 et 1,36 ppm

.EC "  5JHK?JKHA @K ?

F I $

1 O = F=I @A @E ?K J = AKHA @= I =JJHE>KJE @AI IEC =KN KJE EI=JE @AI JEBI @A ? KF =CA AJ @AI ? IJ= JAI ? HHAIF @= JAI FAH AJ @ J=> EH @AI HA =JE I @A FH NE EJ ? H AI F=H AI L= AKHI @AI @ F =?A A JI ?DE EGKAI HA? = J =EI A J  AI IEC =KN @K CH KFA JDO A GK=@HKF AJ @ > E @ = 4, 20 FF AJ JHEF AJ = 1, 31 FF  A IEC = @K CH KFA JDO A F HJ F=H "+ @ K> AJ = 1, 06 FF  AI @AKN IEC =KN @AI O=KN @ > E @ I @=J AI @DO@H C A LE O EGKAI = 6, 97 AJ 5, 78 FF ? KF I A JHA AKN F=H = ? IJ= JA 3 J = 16, 2 0 AJ ? KF I 0 "+ HAIFA?JELA A J F KH 0  + F=H = ? IJ= JA = F KI B=E> A 4 J = 1, 6 0 AJ F KH 0 !+ F=H = ? IJ= JA = F KI CH= @A 3 J = 7, 6 0 L= AKHI IK I= A J @E HA JAI GKE FAH AJJA J @=IIKHAH =JJHE>KJE  A IEC = @K O=K @A 0 "+ = 2, 50 FF =JJHE>K @K A F=HJ F=H = = CEA =LA? AI IJHK?JKHAI @AI ? F I I FH ? @A JI AJ @=KJHA F=HJ F=H AI L= AKHI @AI ? IJ= JAI @A ? KF =CA

5K AJ - 5 2+

#

+DE EA HC= EGKA



 AI @AKN IE CK AJI @AI O=KN @=J AI @DO@H C A @AI CH KFAI JDO A @K ?O? A FA J=C = ! ! EI ?DH AI =EI C >= A A J EI ?DH AI F=H IKEJA @A = FH NE EJ @K =J A @A ?=H> A =IO JHEGKA  O=KN @E=IJ H J FEGKAI = 1, 42 AJ 1, 36 FF  AI IEC =KN @AI O=KN @AI =J AI @DO@H C A 0 #+ AJ 0 $+ =JJHE>K I F=H AI L= AKHI @AI @ F =?A A JI ?DE EGKAI AJ @A = K JEF E?EJ *EA JAH GKA A O=K @A =J A @DO@H C A LE O EGKA A F KI EC @K CH KFA ?=H> O A AIJ A F KI @ > E @ @K B=EJ @A = @ ?= EI=JE A?JH EGKA GKE B=EJ =FF=H= JHA K A =?K A A?JH EGKA IKH =J A @A ?=H> A GKE A F HJA
H EtO O O H O O H O EtO O H

.EC #  , > E @=CA @K

O=K A F KI

EC

@K CH KFA ?=H> 

OA

 % ,= I A

JD=

A HEIGKA AIJ K A JH= IAIJ HE ?=JE

 E EJ

 7 A = = OIA H JH IO JD JEGKA IE F A JHA GKE ? LEA J @A AJJHA A KLHA IK??AIIELA A J  K A H =?JE @A 9EJJEC =LA? A JDO ?=H> JD NO JDO AJHEFD O FD IFD H= A  = @ FH JA?JE @K @E DO@H OIA A E EAK A=K JD= ?=J= OI A F=H ANA F A F=H =?E@A JHE K H =? JEGKA  = FH JA?JE @K CH KFA 0 A F KI K? FDE A ?=H A E I A ? >H  F=H A ?D HKHA @A JAHJ >KJO JHEFD O IE O A  = IK B O =JE = = CKA =?O =JE  @K CH KFA DO@H NO A HAIJ= J F=H A ?D H FD NOJDE ?=H> =JA AI JH= IB H =JE I I J H=IIA > AI IKH = CKHA $ !   A A I=EI F=I H F @HA ,K F E J @A LKA @K >E = E O = ?O? EI=JE =LA? FAHJA @K CH KFA +5 2D AJ = KJ @K =J A @DO@H C A =LA? ? IAHL=JE @K >HA @E I=JKH=JE I ,K F E J @A LKA @K ?= EI A ?AIJ A F=HJEA K A =@@EJE H=@E?= =EHA ! = FHA E HA J=FA AIJ = H =CA @A A )1* AIJ K = H?AKH IA = JAH E CEA @AH A =??AFJ A  ? @EIJE CKA E EJE=JE @A = H =CA ?A GKE AIJ =IIA HECE = E I HECE = = F IEJE @A  A?JH ? E>=J=EHA @= I E JAH @E=EHA EIIK @A =@@EJE @K H=@E?= IKH = ? A =E IE GKA =J A @A ?=H> A # F=JJAI B=?E A E A = GKA IKH A I?D =  @= I A FH @KEJ =  ,= I K FHA EAH JA FI )1* IA ? KFA A H=@E?=KN AJ @E= JA IA K FH ?AIIKI >EA F KI ? F ANA GKA ?A GKE AIJ I?D =JEI ?E =FH I CKHA % - IKEJA K H=@E?=
EI >KJOH EJHE A =HH=?DA K =J A @DO@H C A DO@HKHA @A JHE>KJO J=E F KH @ AH A H=@E?= *K! 5 GKE FAKJ I J KH A J= AH = > K? A @A FH F=C=JE 7 ANA F A @A JAH E =EI I HJEA @A = > K? A @A FH F=C=JE  IAH=EJ A ? KF =CA @A @AKN H=@E ?=KN F=H ANA F A *K! 5 AJ 4 A ?D=K =CA FAH AJ @=KC A JAH = ?E JEGKA @A = JH= IB H =JE - KJHA = @ ? F IEJE @A )1* AIJ B=L HEI A F=H K A =KC A J=JE @A JA F H=JKHA E IA B H A ! AIF ?AI F=HJEH @K A @ ? A JH FEA IJ= @=H@ @A H =?JE AIJ B HJA A J F IEJELA AJ K A =KC A J=JE @A JA F H=JKHA HA @ A JD= FEA E>HA IJ= @=H@ @A @ ? F IEJE F KI C=JELA

5K AJ - 5 2+

#

+DE EA HC= EGKA

Ph Ph P H O O O compos 17 OPPh3 O TFA, H2O, MeOH EtO O

S Cl OPh

Ph

COOEt

EtO O O propanone

OH OH TBDPSCl, imidazole, DMF

EtO O O S compos 18

OTBDPS OPh

EtO O OH

OTBDPS

.EC $  5?D

= @A IO JD IA @K ?

F I &

CN N NC N

N2 (gaz)

CN

Bu3SnH H

CN + Bu3Sn

.EC %  , ?

F IEJE

@A )1* A AJ K
FE CA :

A @ HEL @ J=E AIJ

= B EI K @

AKH @=J

A @DO@H C

! FAKJ E =CE AH = B H =JE @A @E=IJ H EI HAI =K ELA=K @A = ?JE @A ?O? A JH= I =E IE GKA = B H =JE @A ?O? AI $ ?D= I F=H E LAHIE @A = H CE I A?JELEJ @A =@@EJE H=@E?= =EHA AI H C AI @A *= @ME FAH AJJA J A JHA =KJHAI @A KIJE AH = B H =JE @K ?O? A # ?D= I FH ?AIIKI # AN =K EAK @A $ A @  1 F KHH=EJ =KIIE IA @ H K AH K A F O HEI=JE @K H =?JEB K H=@E?= EIIK @K A FHA E HA ?K A IA N= J IKH = @ K> A E=EI @K A IA? @A !  ! = ?O? EI=JE AIJ H = EI A A I KJE JH I @E K A @A = E HA E EJAH AI H =?JE I E JAH ?K =EHAI = JH= IB H =JE E JH= ?K =EHA AIJ = E I H= A JEA D=KJA @E KJE I= LEJAIIA AIJ FH F HJE A A ?A A @K H=@E?= = HI GKA = LEJAIIA @A = JH= IB H =JE >E ?K =EHA AIJ FH F H JE A A =K FH @KEJ @A = ? ?A JH=JE A H=@E?= AJ @A = ? ?A JH=JE A H =?JEB JH I B=E> A =EI JH=L=E AH B=E> A ? ?A JH=JE A E EJA F=I = B H =JE @A ?O? AI DAN=C =KN !  " =E A LEA @A @EHA GKE I=CEJ @K ? JH A ?E JEGKA =EI GKA I =HCK A JI =L= ?AH IE = IJ=>E EJ E @HA @K ?O? A $ ?D= I F=H H=FF HJ K ?O? A FA J=C = AJ = IJ=>E EJ E @HA

5K AJ - 5 2+

#

+DE EA HC= EGKA

!

@K ?O? A ?EI @EIK>IJEJK F=H H=FF HJ =K ?O? A JH= I @EIK>IJEJK !   = = OIA @K J=> A=K @A @ AI  EC AI  AJ  JHA GKA = IJ H I A?JELEJ AIJ E @ FA @= JA @A = =JKHA   K -  @A = ? A @A @ F=HJ ?A GKE IANF EGKA F=H  GKE E>HA J=> E ? B H =JE A J=> E A JHA * AJ , = EBAIJA A J >A=K? KF F KI B=L H=> A , GK * F KH @AI H=EI I IJ HEGKAI LE@A JAI E JAH=?JE I  ! @E=NE= AI F KI CH= @AI @= I * GKA @= I , A ?= EI A E @EGKA GKA = ?H =JE @K ?A JHA =IO JHEGKA @EIJE CK= J EHE@ OH ?E A ' @A I FE HA  IA B=EJ IKH =J A $ L EH CKHA HECE = A I EJ F=H = B=?A =L= J ? @KEI= J ' I EJ F=H = B=?A =HHE HA ? @KEI= J  1 IA > A LE@A J GKA = B=?A =L= J AIJ F KI @ C=C A GKA = B=?A =HHE HA ?A GKE B=L HEIA = B H =JE @A  = = OIA @K J=> A=K  EC AI AJ " JHA GKA F KI 4 AIJ L K E AKN F KI ' AIJ B=L HEI ?A GKE IA > A ? JH=@E?J EHA @= I K A FHA E HA =FFH ?DA =EI GKA  FAKJ E JAHFH JAH B=KJ >EA JH KLAH K A H=EI  F=H K A C A F KI E F HJ= JA HI @A = FOH= E@= EI=JE @A =J A $+ A CH KFA JDO A E JAH=CEII= J @ B=L H=> A A J =LA? A CH KFA +0 4 - HAL= ?DA A A ? FHA @I F=I A AJ @K CH KFA 4 - ?A GKE ? ?AH A E JAH @E=EHA E EJE= EIIK @A = ? A -  I= ? B H =JE FHELE CE A AIJ + AJ - J K KHI ?=KIA @AI E JAH=?JE I  ! @E=NE= AI L EH CKHAI @A  ?  ! !  1 I=CEJ @K A FE HEI=JE A F IEJE @K CH KFA ?=H> O A A ?= EI A AIJ K A IKEJA @A @ FH J =JE FH J =JE =LA? F=II=CA F=H = E =JA F = AJ B H =JE @AI @AKN @E=IJ H EI HAI HI @A = FH J =JE = B H?A JHE?A AIJ I= I @ KJA @ HECE A IJ HEGKA =   EI EHE@ OH ?E A J= J I= I @ KJA F KI IJ=> A GKA I FH ?KHIAKH ? FJA JA K @A = F IEJE @K CH KFA JDO A

 4A ? JH I=JE IO JD
O

=HGKA ?AJJA JH= IB H =JE ? H A @=E AKHI GKA = ?O? EI=JE H=@E?= =EHA AIJ I KI A ?E JEGKA FKEIGKA A FH @KEJ A F KI IJ=> A  = HEJ=EHA @= I AI ? @EJE I @ FE HE ?AIJ @EHA @ GKE E>H=JE JDAH @O = EGKA AIJ E HEJ=EHA @= I AI ? @EJE I @A = IA

MeO O MeOH

O O

O O

MeOH MeO H3C

O + O H H3C

O O H

H3C

H nolate plan

iridomyrmcine

isoiridomyrmcine

iridomyrmcine

.EC & 

?= EI A @A  FE

HEI =JE

@A EHE@

OH

?E A