HAL Id: tel-00776100
https://tel.archives-ouvertes.fr/tel-00776100
Submitted on 15 Jan 2013
HAL is a multi-disciplinary open access
archive for the deposit and dissemination of sci-entific research documents, whether they are pub-lished or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers.
L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.
catalysées par des platinacycles carbéniques
Hélène Jullien
To cite this version:
! !"#$%&'#()*+,&#'-./0* "#$%&!'$#($)*%&!+,-.-&!/&!0*)-1234/! ! 123.4*54*56716891* ! 0)51&6(5&!7*)! 2):;"%*<!==>4?* ! "6!84&!/&!%9$:(&6(-$6!/4!;)*/&!/&! 56714!8*4?*.7>4?74.*54*=@!?>A48.>1B*+98>.-.!5* !"#$%&'%(#)*+%,%-)./0&1%23-) !
B1!54*54*7C7=6>.6DB8>.91>6?.*B?9?1>6.B=471>A4.*
5@B?C?4.*7919=C.B4.*+98*54.*+=91>?97C7=4.*
798EB?>F!4.*
! <,=1&!7)57*)5&!1$41!%*!/-)&#(-$6!/4!')>!?6;&%*!@?ABC"<<B! !"#$%$&$'()'*+%,%)'()#'-&.#$/"0)#'1/$&2)33)#'4567'89:;<' ! 3$4(&64&!%&!.*)/-!DE!6$8&.:)&!DFGD!H!%9B+3C!/&8*6(!%*!#$..-11-$6!/9&I*.&6! #$.7$15&!/&!J! !0)>!0,-%-77&!K"L@MC<!! N6-8&)1-(5!0*)-1!'&1#*)(&1O!0*)-1!P!! A*77$)(&4)! ')>!@*)Q1&!RMNSRMN!! N6-8&)1-(5!0*4%!3*:*(-&)O!<$4%$41&! A*77$)(&4)! ')>!T-6#&6(!+"3?A! L*:$)*($-)&!/&!+,-.-&!/&!+$$)/-6*(-$6O!
<$4%$41&!
"I*.-6*(&4)!
0)>!T-6#&6(!R?C'MC! N6-8&)1-(5!0*)-1234/!GGO!M)1*Q! "I*.-6*(&4)!
')>!?6;&%*!@?ABC"<<B! B61(-(4(!/&!+,-.-&!/&1!34:1(*6#&1!C*(4)&%%&1O! R-U214)2S8&((&!
'-)&#(&4)!/&!(,=1&!
!
!
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
#
F)"=# $&.# I"# ."/".0)"# J=D"1(# ?(.)="**)# +"# /,(4%).# (00&")11)"# +(=$# $%=# 7>&)6"# )1# B# (# 6."$>&"# K# (=$# 1%.$# +"# /"$# $*(D"$# +"# /($*".# L# "*# M# 6&)$# +"# /,(4%).# H()*# 0%=H)(=0"# 6%&.# .7(1)$".#/(#*'8$"#((-%.(*%)."A#?".0)#6%&.#4%*."#D"=*)11"$$"E#4%$#0%=$")1$#"*#4%$#)+7"$A# !,()#-"(&0%&6#(66.70)7#=%$#+)$0&$$)%=$#$&.#1"#$&I"*#>&)#/,%=*#6"./)$#+"#."$*".#/%*)47"# /N/"#>&(=+#0"1(#="#/(.0'()*#6($#*.8$#-)"=A# # !"#."/".0)"#"=$&)*"#*%&$#1"$#/"/-."$#+"#1,7>&)6"#OP#>&"#I,()#."=0%=*.7#(�%&.$#+"#$"$# (==7"$A# #
?"$# 6."/)".$# /%*$# $%=*# 6%&.# 3"16')="# >&)# /,(# "=0(+.7"E# H%./7"# "*# *.(=$/)$# $"$# 0%==()$$(=0"$#$&.#1"#61(*)="#1%.$#+"#/"$#$*(D"$#+"#/($*".A#?".0)#6%&.#*(#D"=*)11"$$"E#*%=# 0(1/"E#*(#-%=="#'&/"&.E#*%&$#*"$#0%=$")11"$#"*#6%&.#1"$#+)$0&$$)%=$A##
#
!"# ."/".0)"# "=$&)*"# ?B.)"/E# <(*'(1)"E# J./"=# "*# <)0%1($# >&)# /,%=*# (00&")11)"# +(=$# 1(# -%=="#'&/"&.#1%.$#+"#/"$#$*(D"$A#?".0)#7D(1"/"=*#9#!7.Q/"#(4"0#>&)#I,()#6($$7#+"#-%=$# /%/"=*$#"=#/($*".#"*#((-%A#
#
,;,"&$'#2%==%/%+"'?# #
0"./%#()*+","&$#*5@#A#*&/%"&&"'#B#8;'$C2;/<#$;5$#27*:;.2#-#0*.%"#8;5.#'*#)"&$%++"''"<#'*# :;&&"#15,"5.<#'"'#/;&'"%++"'<#+"'#8*5'"'#$1(#"$#'"'#2(+%/%"5@#)D$"*5@#E#85%'#-#F*$1".%&"# 8;5.# +"'# 2%'/5''%;&'# "$# ';&# .%."# /;,,5&%/*$%=#E# "$# "&=%&# -# 0(+*&%"# *3"/# 45%# %+# *# ($(# *).(*:+"#2"#8*.$*)".#A#+7*3"&$5."#8+*$%&"#B?#
#
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
#
$
=#$ ,1#"&$ >$ /#+#/?1#/$ #"&.1,#$ @)&?)*$ %-./$ *#&$ &,/.?,./#&$ ?/1&,)**-(/)%516.#&2$ )1"&1$ 6.#$ A81*#2$4.:)""#2$B),5)*1#$#,$C/)"?D$%-./$*#&$+-+#",&$%)&&'&$#"$E@FG<$0#/?1$%-./$7-,/#$ )18#$#,$7-,/#$81&%-"1H1*1,'<$
$
=#$ /#+#/?1#$ 8#$ +)"1I/#$ ('"'/)*#$ ,-.&$ *#&$ (#"&$ &J+%),516.#&$ 6.#$ K9)1$ /#"?-",/'&$ >$ *91"&,1,.,$#,$6.1$?-",/1H.#",$>$*)$&.%#/$)+H1)"?#$6.1$J$/I("#<$
$
C1")*#+#",$ K#$ /#+#/?1#$ +)$ L)+1**#<$ M-.,$ 89)H-/8$ +#&$ %)/#",&$ 6.1$ +9-",$ ,-.K-./&$ #"?-./)('#$>$L)1/#$*#&$',.8#&$6.#$K#$7-.*)1&$#,$6.1$-",$,-.K-./&$','$%/'&#",&<$
0#/?1$ '()*#+#",$ >$ 3"1?#,,#$ #,$ =-N*$ %-./$ *#./$ %/'&#"?#$ #,$ *#./$ )??.#1*$ ,-.K-./&$ ?5)*#./#.O<$
P,$ #"L1"2$ +#/?1$ >$ Q/'(-$ 6.1$ +9)$ )??-+%)("'#$ #,$ &.%%-/,'#$ ).$ ?-./&$ 8#$ ?#&$ R$ )"&$ #,$ #"$ %)/,1?.*1#/$?#&$8#/"1#/&$+-1&<$M.$)&$,-.K-./&$,/-.7'$*#&$+-,&$%-./$+#$/#+-,17#/2$+#/?1<$$ $
!
*/0*+'1*#2,$(0,+2( -.3(
!
,##*/*&( 45-!
! !
#$%! &'&()*%)+,-*%./*)0%! 12,0'0$%! &./.('%,$%! 3.-! 1$%! +,/.45! 1$! /-.0%*/*)06! 3$-+$//$0/! 12.&&,1$-!$0!40$!%$4($!,/.3$!7!1$%!%/-4&/4-$%!&)+3($5$%!&'&(*84$%!)4!3)('&'&(*84$%!3.-! *%)+,-*%./*)0! 1$! %49%/-./%! *0%./4-,%! %*+3($%:! ;$! &$! <.*/6! &$%! -,.&/*)0%! 3-,%$0/$0/! 40! =-.01!*0/,->/!%'0/?,/*84$:!
!
@4! &)4-%! 1$! &$%! 1$-0*A-$%! .00,$%6! &$%! -,.--.0=$+$0/%! )0/! ,/,! ,/41*,%! 1$! +.0*A-$! *0/$0%*B$!.B$&!1*B$-%!+,/.45!1$!/-.0%*/*)0!&)++$!&./.('%$4-%!C3.((.1*4+6!-?)1*4+6!)-6! .-=$0/6! 3(./*0$DE:! F$3$01.0/6! 3$4! 1$! &'&()*%)+,-*%./*)0%! ,0.0/*)%,($&/*B$%! )0/! ,/,! 1,B$()33,$%:!#$!3)/$0/*$(!%'0/?,/*84$!1$!&$%!-,.&/*)0%!0)4%!.!&)014*/!7!0)4%!*0/,-$%%$-! .4! 1,B$()33$+$0/! 1$! B.-*.0/$%! ,0.0/*)%,($&/*B$%! 7! (2.*1$! 1$! &)+3($5$%! 1$! 3(./*0$! &?*-.45:!
!
F$! +.04%&-*/! 3-,%$0/$! 0)/-$! 1,+.-&?$! $/! -,%4+$! ($%! 3-*0&*3.45! -,%4(/./%:! #$! 3-$+*$-! &?.3*/-$! $%/! &)0%.&-,! 7! 40$! 9-AB$! -$B4$! 9*9(*)=-.3?*84$! %4-! (.! &'&()*%)+,-*%./*)0! 12,0'0$%:! #$%! 1*<<,-$0/%! 3-)14*/%! 3)4B.0/! >/-$! )9/$04%6! ($4-! +,&.0*%+$! 1$! <)-+./*)0! .*0%*!84$!84$(84$%!-,.&/*)0%!,0.0/*)%,($&/*B$%!%)0/!-$(./,%:!!
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
#$! &?.3*/-$! QQQ! %$-.! &)0%.&-,! .45! .33(*&./*)0%! 1$! (.! +>+$! +,/?)1)()=*$! 7! (.! &'&()*%)+,-*%./*)0! 12,0'0$%G"6R! 3)%%,1.0/! 40! =-)43$+$0/! )5'=,0,! $0! 3)%*/*)0! 3-)3.-='(*84$:!!
!
"#$%&'()!*!+!",-./&0/12(&0$'&/30!4523,3)0!
! !
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
!!!!!!!!!!!!!!!!!!! ! ! ! ! ! ! ! ! ! ! !
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
#$%&'(#()&! *!+,! -.! '/0&'1(#! 1&! 2)13.%40! )567%&#! 81(! 9)$:0! .0! :;#%..%262.)30&#<&0! "! *#$%&'()*+,=! ! ! ! ! ! ! >0'!(�$:;7(%($0'!:;#%..%262.)30&#<&0'!')&#!3$)3)';'!3)1$!.0!:;2%&(':0!7/1&0!.%$40! ?%$(;#;! 70! $;%2#()&'! (:3.(81%&#! 70! &):@$015! :;#%15! 70! #$%&'(#()&! 0#! 3%$#0&%($0'! (&'%#1$;',!
!
!A3$<'!BC;.(:(&%#()&!0#!;.(:(&%#()&!$;712#$(20D!.0'!7(<&0'CEDF!)1!CEDG!+!')&#!)@#0&1',! !
#$%! &'()*$+$%! ,$! -./0123.(! )$.4$2/! 156*$($2/! 7/-$! ./3*3%1%! )'.-! *6! 8'-(6/3'2! ,$! ,392$%! $/! 3*%! %'2/! %'.4$2/! &'()*1($2/63-$%! ,$%! &6/6*:%$.-%! ;! <6%$! ,$! )6**6,3.(! =!"#$%&'(>?@A!! ! ! !! ! ! !
B2! $88$/C! *D12:2$! (! &3E,$%%.%! (3%! $2! -16&/3'2! 64$&! =FF0G>HF,=IJ&>H! &'2,.3/! $+&*.%34$($2/!6.!,392$!@CG!6*'-%!K.$!*$!-./0123.(!8'-($!%1*$&/34$($2/!*$%!,392$%E@CL?! ! F6-6**9*$($2/C!M0625!6!(3%!6.!)'32/!.2!%:%/9($!&6/6*:/3K.$!./3*3%62/!,$%!&'()*$+$%!,$! -0',3.(!)'.-!*6!&:&*'3%'(1-3%6/3'2!,D12:2$%!$2!,392$%E@CL!=!"#$%&')>?@@!#$!/-9%!<'2%! -1%.*/6/%!%'2/!'</$2.%!$2!/$-($%!,D6&/343/1!$/!,$!%1*$&/343/1?! ! ! ! ! ! ! ! ! !
N2$! 5-62,$! 46-31/1! ,$! %.<%/-6/%! 6! 1/1! (3%$! $2! -16&/3'2! 64$&! *$%! &'()*$+$%! OP0=*3562,>Q*RH! $/! J5S<T"?! U$%! *3562,%! ,.! -0',3.(! %'2/! ,$%! )0'%)032$%! '.! ,$%! )0'%)0323/$%! <3,$2/1%?! U$%! ,392$%E@CL! %'2/! 8'-(1%! ,$! 86V'2! K.6%3! $+&*.%34$! 64$&! ,$%! -$2,$($2/%!&'()-3%!$2/-$!WA!$/!@AAX?! ! ! ! !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! @A!Y?!Z?![-'%/C!T?!#?!['%/$C!67)817)!"(17)9/-7)*+++C!:;;C!\@LE\@W?! @@!F?!Q6'C!Y?!]625C!^?!M0625C!67)817)!"(17)9/-7)*+++C!:;;C!"L_AE"L_@?! MeO2C MeO2C CpRu(CH3CN)3+PF6 -DCM, t.a., 1h 82% MeO2C MeO2C !"#$%&'(' !"#$%&')' (''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''')' X Rh(ligand)Cl 2 AgSbF6 DCM, t.a. 50%-quant. X R R' R
X= O, NSO2Ph, C(CO2Et)2 R= Ph, Ar, Me, Et, CO2Me, CH2Ph
67 *3&('124%#%'(0)89#..,.(0:) !
#$!%&'()*+%$!,-.,.+&!$+/!0$!+1*2()/!3!0$!'.%,0$4$!5$!-6.5*1%!('/*2$!+*%10/()&%$)/!0$+! 5$14!*)+(/1-(/*.)+!,1*+!07*)/$-%&5*(*-$!!!-&(8*/!(2$'!0$!'60.-1-$!(0090*:1$!,.1-!;.-%$-!0$! '.%,0$4$! <=(0090*:1$! ">! ?$! 5$-)*$-! $+/! $)! &:1*0*@-$! (2$'! 0$! '.%,0$4$! A=(0090*:1$! #! :1*! +1@*/!07*)+$-/*.)!5$!07(0'9)$!5()+!0(!0*(*+.)!B6=?0>!C);*)D!07&0*%*)(/*.)!-&51'/-*'$!51!%&/(0! '.)51*/!(1!5*E)$=FDG>! !
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tO2C EtO2C Pd(dba)3.CHCl3 (2,5%mol)
AcOH (5%mol), (o-Tol)3P (5%mol)
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
! ! ! ! ! ! $%! &'()*%+*! ,-./0112#345! *6! ,-.789:;! ,<%)! 5*! ,=+25>'>?(62<%*@! 5-(%A%*B"@;! !"! )*! '(<''<%7*!*%!,=C%*!,*!6A&*!D!!#E!F*!)A)6C?*!+<6<5A6=G/*!?>%6'*!/%*!6'C)!9>%%*!<+6=H=6(E! $%! *II*6! 5*! &'>,/=6! ,*! +A+5=)<6=>%! *)6! >96*%/! G/<%6=6<6=H*?*%6! *%! +=%G! ?=%/6*)! J! 6*?&('<6/'*!<?9=<%6*E!!
!
F<! ,*'%=C'*! &<'6=*! ,*! +*! &<'<7'<&2*! *)6! +>%)<+'(*! J! 6'>=)! *K*?&5*)! ,*! I>'?<6=>%! ,*! ,=C%*)!,*!6A&*!DD!&<'!,>/95*!+>/&/'*!,*)!5=<=)>%)!4B4E!
!
4>??*!%>/)!5-<H>%)!H/!,<%)!5*!$%&'()*!"@!L/'<=!<H<=6!>96*%/!J!&<'6='!,-(%A%*)B"@;!/%! ?(5<%7*!,*!,=C%*)!<H*+!5*!,=C%*!,*!6A&*!D!+>??*!&'>,/=6!?<M>'=6<='*E!8>%!(G/=&*!<!<5>')! 6*%6(! ,*! I<H>'=)*'! 5<! I>'?<6=>%! ,/! ,=C%*! ,*! 6A&*! DD! *%! I<=)<%6! H<'=*'! 5<! )6'/+6/'*! ,/! )/9)6'<6E";!.&'C)!,*!%>?9'*/K!*))<=)@!=5!<!(6(!?>%6'(!G/*!5<!)/9)6=6/6=>%!,*!5-<5+A%*!&<'! /%*!I>%+6=>%!*)6*'!+>%,/=6!*K+5/)=H*?*%6!</!,=C%*!!+!0$%&'()*,!3E! ! ! ! ! ! !
$%&'('))*+! '! ,-'.*/*+0! 1,%)20! 3+! ),'))'+-*/*+0! 1*! 045*! 66! 7'28'+0! 2+0*)(*+2)! 1*8! %'0'.48*3)8!19:)!;!"#$%&'((<=>"! ! ! ! ! !
$%&'()*&!+!,-'*&./!0+!1,&2+(3,)!4*!5650,-7(8)*'!9+&!5+(+06'*!+7!90+(3)*:;<! ! ! ! ! ! !! ! !
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
!
F*((*! 2/(@,4,0,?3*! +! /(/! +9903E7/*! J! 0+! '6)(@8'*! 4*! 5,29,'/'! (&356503E7*'! E73! ,)(! 97! K(&*!3',0/'!+.*5!4*!(&8'!-,)'!&*)4*2*)('!L%&'()$*!+M<!! ! ! ! ! ! !
$%! &'()*+,-,%! &%! .*/0'1%! %20! -0'*'23! (+44%! (/0/*52%-,! %0! (+1&-'0! 6! */! 7+,4/0'+1! &-! (5(*+8-091%!/:%(!;"<!&%!,%1&%4%10=! >?/-0,%2!430/-@!.%-:%10!3A/*%4%10!(/0/*52%,!(%2!,3/,,/1A%4%102B!!(+44%!./,!%@%4.*%! *%!./**/&'-4B!*?+,!+-!*%!A/**'-4=CC! ! ! -6 7/'1#&%/3)4()4%83(0)$#')-,-.%0#&%/3)9:(34/);</%()=6) !
! ! ! ! ! ! ! ! $%&'()*+!*,*-./*+!0*!)1&2(345+!&5&/46'*+!45(!1(1!012)3(+!&7*2!0*+!24-./*,*+!0%3503'-8! 9:!0*!;*)89<!4'!0*!)'(=153'-9#!24--*!2&(&/>+*')+?! ! ! 46 7/'1#&%/3)4()8%-,-./"($&93(0):;/%()*<6)) !
@*+! )1&2(345+! ;&3+&5(! /%4AB*(! 0*! -*+! ()&7&',! 0*! (=C+*8! /*')! -12&53+-*! *(! 0*+! *,*-./*+! +*)45(!.)1+*5(1+!0*!;&D45!01(&3//1*!0&5+!/*!2=&.3()*!EE!0*!2*!-&5'+2)3(?!
! !
!" #$%&'(%)*+,-''(./-0.12)*)320450.67%)* !
@4--*! 54'+! &745+! .'! /*! 743)! &'! ()&7*)+! 0*! /&! .)1+*5(&(345! F545! *,=&'+(37*G! 0*+! 03;;1)*5(+! -12&53+-*+! 0*! 2>2/43+4-1)3+&(3458! 0*! 54-A)*'+*+! -1(=404/463*+! 45(! 1(1! 017*/4..1*+?! @*)(&35*+! 0%*5()*! *//*+! 45(! 01BH! 1(1! '(3/3+1*+! 24--*! 1(&.*! 2/1! 0&5+! /&! +>5(=C+*!0*!-4/12'/*+!5&(')*//*+!4'!0*!24-.4+1+!A34/463I'*-*5(!&2(3;+?!J)43+!*,*-./*+! +45(!04551+!23K0*++4'+?!
! !!!!!!!!!!!!!!! ! ! ! ! ! ! ! ! ! ! ! ! ! ! $%! &'()*%+*! ,*! ,-+./0'1'*! ,*! &/23-%*! ,2%)! /*! 30/14%*! 5! 6789:! /;(%<%*=":>! !"! +<+/0-)0?('-)*!2@*+!1%!A0%!'*%,*?*%3!,*!BCD!*%!,-4%*!!#!,*!3<&*!E!@-2!1%!?(+2%-)?*! &2'!2+3-@23-0%!(/*+3'0&.-/*F!G;213'*)!)*/)!,*!&/23-%*!HI3J'K:!I39/L!*3!I3J'LM!2-%)-!N1*!,*)! 2+-,*)! ,*! O*P-)! HQ/9/R:! S%9/K! *3! T-9/LM! &*'?*33*%3! (U2/*?*%3! /2! V0'?23-0%! ,1! A-+<+/*! ?2-)!2@*+!1%*!?0-%)!A0%%*!2+3-@-3(!+232/<3-N1*F!!
$%&'()*+! ,+! -./)! /! ,&01)2! +3! 45""! 6/! 7832.97+! 2:2/6+! ,+! 6/! ;<=<>/?/,:@/1)3! AB! (3! /60/6:C,+!)77(!,%(3+!&*:3D+!@/1)3+E4#!!
F+22+!@:6&0(6+!2197!0:@*6+G+!+72!0:372)2(&+!,+!7)G!0806+7!+321+6/0&7E!H:3!3:8/(!0+321/6! 2+21/0806)'(+! +72! I:1@&! J! */12)1! ,%(3! &383+<"BK! */1! (3+! 0/70/,+! 1&/02):33+66+! 0806:)7:@&1)7/2):3L.8,1:/186/2):3!;!"#$%&'()=E! ! ! ! ! ! ! $+! 21/)2+@+32! ,+! 6%&383+! (*! */1! 6+! ,)0.6:1(1+! ,+! *6/2)3+! +321/M3+! (3+! 0806)7/2):3! 1&D):7*&0)I)'(+! K<(34/! +2! 72&1&:7*&0)I)'(+E! N3! 7+(6! )7:@91+! +72! :O2+3(! /P+0! (3! 1+3,+@+32!,+!Q"RE!
!
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`A!<3/M!RA!Q2_2(9'2M!637(89)!"(19)*3&9):49)*))+M!;<M!>>"6>>BA! BS!5A!$%)M!RA!I%M!QA!a9M!bA!W824DM!637(89)!"(19)*3&9):49),--,M!=>M!BCSc6BC>dA! ! !"#$%&'((' O R1 O R1 Rh(cod)Cl 2 / (R)-BINAP AgSbF6 DCE, t.a. R2 R2 >99% ee
R1= aryles, Me, nC4H9, COPh, CH2OH,
CH2OMOM
R2= H, Me, Et, OMe, OH
#$%!%&''(%!)*+$,&%!-.,%!/$!-01$/)22$3$,+!-$%!'4'/)5%)3065%.+5),%!-70,4,$%!$,!1$6%5),! .%430+658&$!),+!'),-&5+!,.+&6$//$3$,+!/$%!'9$6'9$&6%!:!&+5/5%$6!'$%!30+9)-)/);5$%!2)&6! /.!%4,+9(%$!-$!')32)%0%!0,.,+5)$,65'95%!-75,+06<+=!>&$/8&$%!$?$32/$%!%),+!260%$,+0%!'5@ .26(%=!
!
#708&52$! -$! A9.,;! .! .22/58&0! /.! 30+9)-)/);5$! :! /.! %4,+9(%$! -7B@30+94/(,$@C@ *&+46)/.'+),$%! 0,.,+5)2&6$%=DE! F,$! %4,+9(%$! G)63$//$! $,! 8&.+6$! 0+.2$%! -$! /.! HIJ@ 25/)'.625,$! $%+! ./)6%! 26)2)%0$=! K$++$! 3)/0'&/$! 260%$,+$! -$%! 26)2650+0%! 29.63.')/);58&$%!5,+06$%%.,+$%!$,!)29+./3)/);5$!,)+.33$,+!H!"#$%&'()J=! ! ! ! ! ! ! !
#70,4,$' *+! '4'/)5%)3065%$! $,! 260%$,'$! -$! LM9HKNOJK/P"Q! -$! H6J@RSTUV! $+! -7&,! %$/! -7.6;$,+! $,! 3)5,%! -$! -5?! 35,&+$%! $,! B@30+94/(,@C@*&+46)/.'+),$! G),'+5),,./5%0$Q! .1$'! &,!6$,-$3$,+!-$!WWX!$+!&,!$?'(%!0,.,+5)30658&$!%&2065$&6!:!WWX=!
!
$%! &'()*+(,-*-.! +/&()/.! .&0! 1*)2/.! %3.4! 5-! ).-+.2.-0! +.! 678! .0! 5-! .94,&! /-%-0(*2/)(:5.!+.!;;8<!
!
$=/:5('.!+.!>*&0.#6!%!+/3.?*''/!5-!&@&0,2.!4%0%?@0(:5.!'*5)!?%!4@4?(&%0(*-!+=/-@-.&ABC7! '*)0%-0! 5-.! 1*-40(*-! /0D.)! +=/-*?! &(?@?/<! E.&! /-@-.&! 4@4?*(&*2/)(&.-0! .-! ')/&.-4.! +.! FG6HAI>JKAL.M'D*&NO+GP>1H"! +%-&! 5-! 2/?%-M.! +=/0D.)! +(/0D@?(:5.! .0! +=%4(+.! %4/0(:5.! %3.4!+.!Q*-&!).-+.2.-0&!G7R!S!;#8H!.0!+.&!.94,&!/-%-0(*2/)(:5.&!4*2')(&!.-0).!R#!.0! ;B8!G!"#$%&'()H<! ! ! ! ! ! ! ! ! ! ! !
$%&'()(*+'(,-! ./! 00612345627/89:,*1;.0<4=1"! >,??/! >+'+)@*/&A! 9/A?/'! )+! =,A?+'(,-! .%&-! >@>)/! B! >(-C! >:+(-,-*! +D/>! &-! /E>F*! G-+-'(,?GA(C&/! ./! HIJ! /'! &-! A/-./?/-'! ./! HKJL!
! !
!!!" #$%&'()*$%+ !
M&! 'A+D/A*! ./! >/! >:+9('A/N! -,&*! +D,-*! ?,-'AG! 9+A! C&/)C&/*! /E/?9)/*! )+! D+A(G'G! /'! )/! 8A+-.!9,'/-'(/)!*@-':G'(C&/!./*!AG+>'(,-*!./!>@>),(*,?GA(*+'(,-!.%G-@-/*L!
!
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
$+! >@>),(*,?GA(*+'(,-! G-+-'(,*G)/>'(D/! +! =+('! )%,RT/'! ./! )+! ':F*/! ./! 3/)9:(-/! 5A(**@! 0"UUK2"UUH1!/'!T%+(!?,(2?V?/!9,&A*&(D(!>/*!G'&./*!+9AF*!+D,(A!9+A'(>(9G!+&E!'A+D+&E!./! 3/)9:(-/!+&!>,&A*!./!?,-!*'+8/!./!6+*'/AL!!
!
$/*! >:+9('A/*! *&(D+-'*! 9AG*/-'/-'! )%/**/-'(/)! ./! ?/*! 'A+D+&E! ,A(/-'G*! D/A*! )/! .GD/),99/?/-'! ./! >+'+)@*/&A*! >:(A+&E! ./! 9)+'(-/! /'! )/&A! &'()(*+'(,-! .+-*! ./*! AG+>'(,-*! ./!>@>),(*,?GA(*+'(,-!.%G-@-/*2SNK!/'!2SNI!/-!.GA(DG*!R(>@>)(C&/*L!!!
! ! ! ! ! ! ! ! ! $%&!'()(%&*+,#!-./0.123(2!4(!5'2'1.'6'/%(2!73(&!63!-538(%!94:!1%6:%!6;.6'<:(%!=!63!21:06%! 6:3:&.(,! -)-6.:&./'1:&%(2! %(! 01'&%(-%! 7%! 7:-56.141%! 7%! 0632:(%! 73(&! 6%! 2.64>(%! =! ?@AB! 0.41! <.1/%1! /3C.1:23:1%/%(2! 6%&! D:-)-6.5%02>(%&! -.11%&0.(73(2&! EF-5'/3! "3GHI@! $%&! 7:>(%&*+,J!1'&4623(2!7;4(%!-)-6:&32:.(!K*(;/*5%<!7%!6;'()(%!&4:L:2!7;4(%!&:/06%!-.4041%,! &.(2!.D&%1L'&!%(!943(2:2'!21>&!<3:D6%!E+!=!+KM!&%6.(!6%&!&4D&2:243(2&GH!!
!
$%! &.6L3(2! &%/D6%! C.4%1! 4(! 1N6%! :/0.123(2! 73(&! -%&! 1'3-2:.(&H! O(! %<<%2,! O-53L311%(! 3! %<<%-24'! 7%&! 1'3-2:.(&! 3(36.P4%&! %(! 01'&%(-%! 7%! 7:-56.141%! 7%! 0632:(%! 73(&! 6;3-'2.(%! EF-5'/3!"DGHI+!B%!&.6L3(2!%(2138(%!63!<.1/32:.(!-.//%!01.74:2!/3C.1:23:1%,!7;4(!7:>(%* +,I!!%2!63!<.1/32:.(!74!D:-)-6%!-.//%!01.74:2!/:(.1:23:1%H! $%&!'()(%&!(%!-./0.123(2!03&!7;5'2'1.'6'/%(2&!-.(74:&%(2!4(:94%/%(2!=!63!<.1/32:.(! 7%!7:>(%&*+,IH!! ! !" #$%&'()*+, !
! ! ! ! ! ! ! ! ! ! ! ! ! ! $%&'()*!+,!-.+&/0*-,1!2,!+3+2,!+&4&234056,!,*4!0/040.!'&(!2&!+77(80/&407/!86!'2&40/,!*6(!2&! 4(0'2,! 20&0*7/9! :,44,! 8,(/0)(,! ,*4! &27(*! &+40;.,! ;0*! <! ;0*! 8,! 2%&880407/! /6+2.7'=02,! 8,! 2%72.>0/,1! +,! 560! 0/8604! 2&! +3+27'(7'&/&407/! 8,! 2%72.>0/,! ,/! >7(-&/4! &0/*0! 2&! *4(6+46(,! ?0+3+2056,!!"#9!@60*!&'()*!-0A(&407/!8%6/!'(747/!,4!.20-0/&407/!86!'2&40/,1!7/!7?40,/4!2,! ?0+3+27=,'4)/,9!!
!
$&/*! 2&! *604,! 8,! +,! '&(&A(&'=,1! 56,256,*! .468,*! 4=.7(056,*! ,4! ,B'.(0-,/4&2,*! 8.+(04,*! 8&/*!2&!2044.(&46(,!*7/4!'(.*,/4.,*!'76(!+=&56,!.4&',!86!+3+2,!+&4&234056,9!
!
#; <-&%4#&%/3)5().6#.-,3() !
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
H8! %+'! $5**.! -.%! 8%+! $5/68%7%+! M'=HH@D(8$:*%! +5*'! '&A+! ,8%$'&56F)8%+! %'! 6%.1%*'! N'&%! 3($)8%/%*'! (''(-.,+! 6(&! 0)33,&%*'+! *.$8,56F)8%+;LL4LO! PQ&+'*%&! (! 0,$&)'! $%+! $5/68%7%+D?! $(')5*)-.%+!$5//%!,'(*'!0%+!$5/68%7%+!?D($)0%+;LR!!
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
! ! ! ! ! ! ! ! !
$%&'()*+,-&.&*)! !"#! /0'-1&(! .1! -&2')345"5! 6*0-1&(! -)! +,(.(728)! -)! 9%,':');! $%&'()*+,-&.&*)!!"$5!<1.'(!=!91&5!6)*+)(!9.!>0*+.(&0'!-1!?&/:/907)6(2');!$%&'()*+,-&.&*)! !"%! /0'-1&(! 60()'(&)99)+)'(! =! 1'! /0+608,! /:/9&<1)! =! @! /7.A'0'8! <1&! '%.! ,(,! +&8! )'! ,B&-)'/)!<1)!*,/)++)'(!6.*!CD*8(')*;EF!!
G%.6*28!9)8!/.9/198!-)!H0*&.'05!9%&'()*+,-&.&*)!/:/906*06.'&<1)!!"$!)8(!&881!-)!9%.((.<1)! -)!9%.9/2')!81*!9%.9/:')!./(&B,!)'!#3&%!-1!+,(.9;!$.!/:/9&8.(&0'!6*0/2-)!-)!>.I0'!/0'/)*(,)! )(!9,J2*)+)'(!.8:'/7*0');!$0*8<1)!KLM!)(!NLOP85!/)(()!,(.6)!-)!/:/9&8.(&0'!Q3(35/!)8(! (*28! )R0(7)*+&<1)! S3"E5FT! U/.9V+09W! )(! 9%,')*J&)! -%./(&B.(&0'! 601*! .(()&'-*)! 9%,(.(! -)! (*.'8&(&0'!)8(!*)9.(&B)+)'(!>.&?9)!S@5FQ!U/.9V+09W;!!
-; <%='#&%/3)56>3)$'/&/3) !
$%&'()*+,-&.&*)! !"#$ )/(! -)! (01)! 2.*3,'45-)! )(! 6.! /73&*! *.1&-)+)'(! 7')! +&8*.(&4'! #9:! -%;0-*48<')!147*!24'-7&*)!.7!2.(&4'!%=!!
!
>)/! )?1,*&)'2)/! -)! +.*@7.8)! .7! -)7(,*&7+! 4'(! 1)*+&/! -)! 24'A&*+)*! B%)?&/()'2)! -)! B%&'()*+,-&.&*)!!"#$)(!B.!+&8*.(&4'!#9:!-7!1*4(4'=C:!!
>.'/! 7'! 1*)+&)*! ()+1/! B%,'0')! &&! =(1D-&-)7(,*,! )'! 14/&(&4'! 1*41.*80B&@7)! .! ,(,! +&/! )'!*,.2(&4'!.6)2!-7!-&2;B4*7*)!-)!1B.(&')!EF2;,+.!GH=!! ! ! ! ! ! ! !
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
T'! .(4+)! -)! -)7(,*&7+! .! ,(,! &'24*14*,! -)! A.U4'! +&'4*&(.&*)! +.&/! /,B)2(&6)+)'(! )'! 14/&(&4'!MD"=!$)/!1*414*(&4'/!-)!1*4-7&(!'4'!-)7(,*,!Q!1*4-7&(!-)7(,*,!/4'(!B)/!+V+)/! @7)!-.'/!B%)?1,*&)'2)!1*,2,-)'()!E"!N#H=!! $)/!2.B27B/!>OW!/788<*)'(!@7)!BX;0-*48<')!@7&!+&8*)!)/(!7'!1*4(4'9!/.!2;.*8)!,(.'(!-)! YZ9"[S=!! ) N D D Ts N N D D D H Ts Ts PtCl2 cat. Toluène (3:1) N H H Ts N N H H H D Ts Ts PtCl2 cat. Toluène D2O (1 éq.) (3:1) '()*+,$-$ '()*+,$.$
&&$ $ $ $$$$$$$&/,$ $$$$$$$$$$$$$$$$$$&/0
$ $ $ $
!
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
V)-,2)-(! -A-*9,-(! 6-! .7.,50(5*'&0(/105%! 68'%7%-(DO+C! -%! @0.7.,5:-91E%-(! (5%1! 9&'(-%1'(!6/%(!.-!9/&/G&/9:->!F-(!.5*9,-A-(!*'1/,,02)-(!,-(!9,)(!.5)&/**-%1!)10,0('(! 95)&! .-(! &'/.105%(! .5*95&1-%1! 6)! 9,/10%-! 5)! 6-! ,85&>! W,! -A0(1-! 2)-,2)-(! -A-*9,-(! 6-! 35&*/105%! 6-! @0.7.,5:-91E%-(! /4-.! 68/)1&-(! *'1/)A! 2)-! ,-! 9,/10%-! .5**-! ,-! &:560)*US+UO+!,80&060)*U#+U"+!,-!G/,0)*UR!5)!,-!*/%G/%E(-UU>!
!
#; <,3&"=0()5()52'%420)$/.,-,-.%>?(0)$#')-#&#.,0()@).6/') !
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
! ! ! !
2'! 0;0&?<'! 9(&(6;&%@$'! (! 54(6'<',&! 8'*<%0! -7:C&',%*! (+'9! $,! C:,! *',-'<',&! $,! 35&5*:9;96'!86$0!9:<86')'!9:<8:*&(,&!@$(&*'!9;96'0!I$0%:,,50!D#935<(!EJFA! ! ! ! ! ! !
! ! ! ! ! ! ! ;< =,3&">0()5()52'%420)$/.,-,-.%?@(0)$#')-#&#.,0()#@)$.#&%3() ! $%&'('))*+!'!,-%)./!0'!12)3'/.2+!,*!%23425-5!/).%6%0.78*5!9!4')/.)!,:-+6+*5;-/&*)5!2<!0'! ,28=0*!0.'.52+!*5/!)*4)-5*+/-*!4')!8+!-/&*)!,:-+20!%6%0.78*!>?%&-3'!@#ABCD!! ! ! ! ! !
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`K!B=*17(!$K!WK!V*<62(!;<)='><)!"(1<)!"#"(!?:(!GDX; GD#K! N Ts N Ts PtCl2 (5 mol%), CO toluène, 80°C N Ts N Ts 63% $%&'()*#+* $%&'()*#,* **********-,* * * * * * ******-.* N Ns O Cl Cl N Ns O Cl Cl N H O Cl Cl .H3PO4 GSK1360707F PtCl2 (3,5 %mol) toluène, 80°C 93%
1- Et3SiH, TFA, toluène, t.a.
92%
2-(i) HS(CH2)2CO2H, LiOH, DMF
(ii) H3PO4, PrOH
!" #$%&'()*+,$*%*'()+$-.&'(/.+, ! #; <=(1$.(0)5().#).%&&2'#&>'() ) • $%&%'()*+,)!-!'./,/0/+1! !
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
$%&'()*%(! +! ,*-%)! ./0*1%! &.%(! 234567&809-*! .%! :5;*<=>?:! @"AB! *0! ::B! (*$&*,0)C*D*10E!*0!-'FG(*D*10!$%&'()*%(!+!,*-%)!./0*1%!&.%(!23:5=-=>?:!@#:BEH!
!
I*7%,.%&! &-%$! (',*DD*10J! KD.%()J! K%/*(0J! L71M.1! *0! N*1$0*(/71O>4! .10! '0%M)'! -*$! DPD*$! ('7,0).1$! ,707-9$'*$! &7(! -Q)()M)%D! D7)$! *1! $%)C710! %1*! $0(70'F)*! M)RR'(*10*! @S,8'D7!TUEH!V1!*RR*0J!-7!,8)(7-)0'!1Q*$0!&7$!7&&.(0'*!&7(!%1!-)F71M!M%!D'07-!D7)$!&7$!%1! ,.10(*! ).1! ,8)(7-H! W*! ,.D&-*X*! M*! Y7$O7! Z[(=-@=<E@\\8"E4]! *$0! ,.D/)1'! 7C*,! %1! $*-! MQ7(F*10!MQ%1!7,)M*!&8.$&8.()^%*!,8)(7-!M'()C'!M%!/)17&80.-!"J"5M)$%/$0)0%'H!_*!0(G$!/.1! *X,G$!'1710).D'()^%*$!@`7/-*7%!4J!UT5a"BE!.10!'0'!./0*1%$!M71$!-7!,9,-.)$.D'()$70).1! MQ7--9-$%-R.17D)M*$! &(.&7(F9-)^%*$! 1*! &('$*10710! &7$! M*! $%/$0)0%710! *1! &.$)0).1! 0*(D)17-*!M*!-Q.-'R)1*H! ! ! ! ! ! ! ! !
!"#$%& '(& '%& ')*+),)*-& ))&
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
! ! ! ! ! ! ! ! ! !
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h (5 %mol) NaBArF 4 (10 %mol) O Ph Ph Ph O Ph DCE, 20°C, 12h 84%, 99% ee F F F F R R Rh P Ph Ph Ph R=CH2OCH2OCH3 Me
Représentation sous forme de quadrants
! ! ! ! ! ! ! ! ! •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
$*&&*! 2]2*! )(;&<?)*! %! 7&7! ,7%'8)7*! *;)+8&*! %E*1! 3'+)! 5*! )+11?)! 3%,! W^,)&;*,A"\! 0*)! 1/23'*4*)! 5./,! 5*! &(3*! O_9+$'V! /`! O_! *)&! +;! 3</)3</,%2858&*! 57,8E7! 5+! X900GOV! /;&!
!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! BC!$AH@A!$<%/V!0A!I*'&,%28V!ZA!aA!X/+''*1V!bA!@81<*'*&V!!"(1=)!/11;3=)!""#V!B\ccHB\\#A! O Ar2 O ! ! ! Ar1 Ar1=Ph, Ar1=Ph, Ar1=Ph, Ar1=3,4-(OCH 2O)C6H2, Ar2=Ph, 34%, ee = 98% Ar2=4-MeOC 6H4, 47%, ee = 96% Ar2=4-NO 2C6H4, 39%, ee = 96% Ar2=Ph, 51%, ee = 90% Ar1 Ar2
Au /L* (1 mol%), AgOTf (2 mol%) toluène, t.a., 1-16h MeO MeO Ar2 P P Ar2 AuCl AuCl Au /L* = Ar=4-MeO-3,5(t-Bu)2C6H2 Rh P Ar2 Cl O O R1=Ph, R1=Me, R1=Me, R1=Me, R1=Me, R2=Me, R2=H, R2=H, R2=H, R2=H, R3=H, R3=Ph, R3=4-MeOC 6H4, R3=CH2OSiMe2tBu, R3=Me, R4=H, 84%, ee = 92% R4=H, 84%, ee = 91% R4=H, 76%, ee = 98% R4=H, 65%, ee = 90% R4=Me, 44%, ee = 91% Ar=t-BuC6H4 ou 3,5-t-Bu2-4-MeOC6H2
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
!
;< ='#4#>?) #3&2'%(>'0) (@@(-&>20) #>) .#;/'#&/%'()+) -/1$.(?(0) 5() $.#&%3() 5() $'(1%A'() B232'#&%/3::)
)
• U&4)%.-,-(5.!>4.4&,2%! !
$%&%'()*$+,-'(.,! /,! 0(-1-+)2"343567,8'9%,*! :&(*! &;-;%! ,<,:8+,! %=;'(+(*,! /;! 8+&'(%,>! ,<-,8'()%! ?&(',! /,*! '@&.&;<! /,! %)'@,! $A;(8,3! B,*! -1-+)(*):$@(*&'()%*! $'&%'! '@9*! ?)@',:,%'! *;0*'@&'C! ,'! :$'&+C/$8,%/&%',*>! +=;'(+(*&'()%! /=;%! :$'&+! -)::,! +,! 8+&'(%,! 8);@@&('!8,@:,''@,!;%,!,<',%*()%!/;!-7&:8!/=&88+(-&'()%!/,!-,*!@$&-'()%*3!
!
$%&! '()*+%,%&! -%! *+./01%! /203'((2-(114&! '(156&! %1! &607.1/! +.! )8)%! &/2./490%! .7.0%1/! 4/4!-4'20/&!*.2!:.914!;<'=4).!>?@A! ! ! ! ! ! ! ! !
---!"---!#-! ! ! ! ! ! • #$%&'()*!+*)!,-./0*1*)!+*!/02&3%*!+*!4(5*!67%752&3-%! !
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
!
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xylyl-Binap)PtI2 (10%), PMe3 (10%), AgBF4 (25%) MeNO2 X=CH2 56%, 92%ee
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
!
Q4!<1)H46)(0!4=)46&!&*(!8'&!*(0H02)*2/0H)&!H0*86(4'(!3&!6E4HH4'M&/&'(!'2'!564'!3&!784(H&! MH285&*! 3)*52*0*! 54H! 54)H&*! 48(28H! 3E8'! 4=&+! Q&! <4*! 6&! 568*! <2''8! &*(! <&68)! 3&! 6E4(H252)*2/0H)&!3&*!P)510':6&*!/'&"/G*8P*()(80*+!! ! ! ! ! ! ! !
'()*+,-..-!$! %&'()! *+,-! .'/! /'..0/1! 2! *+',1/)! 3'-4! ,-! &%/0%/$! -)! 40-1! .'4! 4,.)/.04'5*)46! 7%! *'! .804.8%-)!)41!'98%/'*)$!"!)1!!!40-1!3)4!:-'-1%0&;/)46!<'-4!-01/)!9'4$!*'!3%.804.8%-)!)41! 98%/'*)!30-9!"!)1!!!40-1!3)4!3%'41:/:0&;/)46! ! =-)!('&&)!3)!90&.*)>)4!40,4!*'!?0/&)!3)!.'%/)4!3)!3%'41:/:0&;/)4!'!:1:!4@-18:1%4:)! .'/!<)*.8%-)!A/%44@6!B,)*C,)4!)>)&.*)4!40-1!30--:4!3'-4!*)!1'5*)',!4,%D'-16! ! ! ! ! !
#$%&#'&()*+,-./.0& #.12.+.13& #435*&"6!&
E)$!F8!G784H! I"J! K!LK! E)$!MNOF8!G789H! PQJ! K!LK! MNOF8$!1RA,!G78)H! IQJ! PK!LP! MNOF8$!M@!G782H! S#J! K!LK! T'.8MNO$!M@!G78.H! USJ! K!LK! :49-.4;&<&
! ! ! ! ! ! ! ! ! !
$%! &'()*+'%! ,-./&! ,0')*! 1)! &2(! 13,.42%*5! &2)(2! (,! &').62! 12! 67+.,(+*8! ,--'.*82! -,.! (,! 1+-7'&-7+%2! -2.&+&*29! :,! ;'.<2! *.+=6''.1'%%82! 1)! 6'<-(2>2! 8*,%*! (32&-/62! 6,*,(?*+@)2<2%*! ,6*+A2! 2*! &*8.8'67+<+@)2<2%*! (,B+(25! (3)*+(+&,*+'%! 12! <8(,%42! 12! 1+,&*8.8'+&'</.2&! ')! 12! 6'<-(2>2&! 1+,&*8.8'+&'<8.+@)2<2%*! -).2&! %2! 67,%42! -,&! (,! &*8.8'67+<+2!12!(,!.8,6*+'%9!C26+!,!8*8!A8.+;+8!2>-8.+<2%*,(2<2%*9!
!
• $A,(),*+'%!1,%&!(,!.8,6*+'%!12!6?6('+&'<8.+&,*+'%! !
:2&! 6'<-(2>2&! 12! -.2<+/.2! 48%8.,*+'%! '%*! 8*8! *2&*8&! 1,%&! (,! .8,6*+'%! 12! 6?6('+&'<8.+&,*+'%!13,((?(,<+12&!-.'-,.4?(+@)2&!2%!D=,E,B+6?6('F"9G9HI72-*/%2&!1'%*!)%! 2>2<-(2! .2-.8&2%*,*+;! 2&*! 1'%%8! 6+=12&&')&9! :2&! 6'<-(2>2&! 1'%%,%*! (2&! <2+((2).&! .8&)(*,*&! 2%! 6?6('+&'<8.+&,*+'%! 8%,%*+'&8(26*+A2! &'%*! 12&! 6'<-(2>2&! -'.*,%*! )%! JKC! 1+&&?<8*.+@)2!LMG!N!MOP!,67+.,(!2*!)%2!1+-7'&-7+%2!67+.,(25!(,!L;5!;P=C7+.,-7'&9! ! ! ! ! !
! ! ! ! ! ! $%!&'()*+%!,-(.%!/+!0(-/,%!)%+123%!345!6!37'1-.%!%.!8-(9%!/+!&2&3%!6!:4;!&<'=+-+:!'>%&!3%! 95.'3!?-(.<-95.'33'.4-+!@/!,<5+23%AB!$%!C/'.(4*9%!340'+@!%:.!/+!4-@/(%!C/4!,-/(('!D.(%! ,4*05! ,'(! /+! :%3! @7'(0%+.! '84+! @%! 34)5(%(! 3%! :4.%! @%! &--(@4+'.4-+! +5&%::'4(%! 6! 37'&.4-+! &'.'32.4C/%B!
!
!" #$%&'()*+*&+,-.-,&/.0)-&01%+ !
#; <,3&"=0()5(0)0(.0)56%1%5#>/.%?1) !
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
!
$,! ! (%/6*8+%! @.*%! (%! &C01A8&%! %&1! /1*'*&4%! 2./3! *013.(/*3%! &/3! '),-.1%! (%&! D3./2%&! @.'/+*0%/6B! (.01! '%&! A,'.D40/3%&! &.01! (%! +,/@,*&! ,D%01&! (),'EC',1*.0<! W,0&! 5%! 5,&B! *'! >,/1!(),7.3(!>.3+%3!')*+*(,-.'%!&/7&1*1/4<! ! ! ! ! ! ! N N N N I OMs OMs I MeCN, reflux 90% NH2 glyoxal, CH2O H3PO4,NH4Cl H2O, dioxane 28% #,'/2-+34+ #,'/2-+35+ 63+ N H N N N I N N I R' X OMs I NaH, DMF quantitatif R'X MeCN, reflux I1,R'=Me, X=I, 90% I2, R'=Et, X=I, 89%
! ! ! ! ! !
$%&! '%()%*%(+&! )%! &,(+-.&%! )%&! /0*12%3%&! &0(+! 40(&! )5(&! 26%(&%*42%! 7%(+'%! "8! %+! 98:;!-0'*<&!5=%/!25!1-0&1-<(%!7;;>?@AB!A0C'!C(%!*D*%!1-0&1-<(%E!2%&!=5'<5+<0(&!)%! &C4&+<+C5(+&!&C'!265F0+%!)C!/5'4.(%!(6<(G2C%(/%(+!15&!&<H(<G</5+<=%*%(+!2%!'%()%*%(+!%(! /0*12%3%B! ! 5< !#'#-&2'%0#&%/30) !
$%&! &1%/+'%&! I?J!KLM! %+!LKA! )C! /0*12%3%! !"#! /0*10'+5(+! 25! 7=;>A->N<(%1<(%! )0((%(+! )%&!/0(&+5(+%&!)%!/0C125H%!/5'5/+O'<&+<PC%&!Q>M>A!)%!K#9!RF!10C'!2%!/5'40(%!/5'4O(<PC%! %+!K>A>A+!)%!Q9"8!RFB!!
#$%&!'()'%*!+,-!.-$/0&,-!$12,*%-3!4,-!'$*-2)*2,-!+,!'$%54)6,!;#7#2!-$*2!+%!/8/,!$&+&,! +,! 6&)*+,%&9! :)! +.)-2;&;$-;4,'2.<.2;! +,! 4)! -=*2(0-,! +,-! '$/54,>,-! *,! +;5,*+! 5)-! +,! 4?,*'$/1&,/,*2!+%!')&10*,!/).-!54%2@2!+,!4)!5($-5(.*,!%2.4.-;,9!
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
(; <(0&0)-#&#.,&%=>(0??9@A) ) $%&!'()(*+&%,-&!./'-0)&!.(1&!*%&!2(-(3-(24%&!2-/'/.%1)&!51)!/)/!)%&)/&!.(1&!*(!-/(')051! 65.7*%!.%!'+'*50&56/-0&()051!.%!*8(**+*2-52(-3+*(60.%!%1!9:(;(<0'+'*5=>?@?AB4%2)71%?! ! ! ! ! !
!"#$%&' ()*+,)-"&' ./' 0*1,2&3&' .&"4&1&"#+' 567'
&&' 567'
@! CBD:EFG! E%! 08' >A! A!
H! E%! 09:' I9! #"! 9! CBD:E515245&! J)! 09;' I9! K9! >! E%! 0<:' LL! I9! "! J)! 0<;' L@! I>! K! CCD:G4:M01%201%!
NOHG4! 0<=' IA! IK!
#! @P@:.024/1+*:DPD:<0&CCCD:@:
24/1+*/)4+*D245&2401(601%! E%! 0>' "H! "@!
?:;2&:@'A'
!
! $!%&'()'!*+!,+-!'.-/0(&(-!%'.0)1)2&)'+-3!0+-!*+/4!5&1)00+-!*+!,61%0+4+-!%0&()2&,7,0)8/+-! 8/)! *622+2(! 0+-! 1+)00+/'-! '.-/0(&(-! 62(! .(.! .(/*).+-! %0/-! +2! *.(&)09! :+-! ,61%0+4+-! ,61%6'(+2(! -6)(! /2+! %;6-%;)2+! *+! (7%+! <)2+%)2+! -6)(! /2! %;6-%;6'&1)*)(+9! =+-! *+/4! %'6,;&)2-!%&'&>'&%;+-!-62(!,62-&,'.-!?!0+/'!.(/*+9! ! ! !" #$%&'()(*+,(+-.%(+/0102345$1+,(+46&(+&'3451(7851(&51(+ ! #; <(0&0)-#&#.,&%=>(0?::9@@) !
$%&!'()(**%!'+,-./%)!01234!5)6.*7!8+%97.*%:,;-<3!==!8>4!>?@:?,*4!7%?9A!B%!-57%*7,(*!8>C4=!%7!>D4E!?,*F! $G&!'()(**%!'+,-./%)!H04!5)6.*7!8+%97.*%:,;-<3!=E!8I4!>?@:?,*4!7%?9A!B%!-57%*7,(*!8>D4J!%7!>=4=!?,*F!! $K&!'()(**%!'+,-./%)!01234!5)6.*7!8+%97.*%:,;-<3!==!8>4!>?@:?,*4!7%?9A!B%!-57%*7,(*!8>>!%7!>I!?,*F!! $+&!'()(**%!'+,-./%)!H'4!5)6.*7!8+%97.*%:,;-<3!E!8I4!>?@:?,*4!7%?9A!B%!-57%*7,(*!8!>J!%7!>C!?,*F!
!
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
!
;< =2&('1%3#&%/3) 5() .#) -/3>%?@'#&%/3) #;0/.@() 5(0) #A#;%-,-./BCD8DEF"($&G3(0) (&) ",$/&"G0()56%35@-&%/3)#0,12&'%H@(IJ)
!
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
!
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h toluène,60°C, 18h N O Ph (1R,6S,S) Ns Ns cat (4 mol%), AgBF4 (12 mol%)
Pt I PPh N N Ph cat = PtCl2, 90°C, 15%, 55:45 cat= C3c , 60°C, 85%, 90:10 $%' $&' I O Ph HO O Ph N O Ph HO Pd(PPh3)2Cl2, CuI pipéridine, toluène, 35°C 82% NH Ns DIAD, PPh3, THF 18h, t.a. 51% OH + OH I (R) (S) 97% ee DEAD, PPh3 toluène, 0°C puis t.a.
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h toluène,60°C, 18h N Ph (1R,6S) Ts Ts cat (4 mol%), AgBF4 (12 mol%)
