Tandem ring‐opening–ring‐closing metathesis for functional metathesis catalysts
Texte intégral
(2) 3..,02%+# +", .
(3) 2!0%(1? +(72%( #0 ! 1,(4!+21 5!0! .30$1! "0,* ,+!75!(( ,0 %#*C( 0%$ + 5!0! 31! 5%2$,32 "302$!0 .30%"%2%,+@ 07 .70% %+! ,4!0 *,(!3(0 1%!4!1 51 .30$1! "0,* %#*C( 0%$ 5%2$ 2$! $%#$!12 .,11%(! .30%27 + 31! 5%2$,32 "302$!0.30%"%2%,+@ 031%+%2%2,01/+ 1= %7(,.!+2 %!+!=!2$7(4%+7(!2$!0 + (( ,2$!0 1202%+# *2!0%(1 5!0! .30$1! "0,* %#*C( 0%$ 3+(!11 122! ,2$!05%1! + 31! 5%2$,32 "302$!0 .30%"%2%,+@ 6,CC*!2$7(+,0,0+!+! %*% ! E
(4) F5117+2$!1%8! 10!.,02! .0!4%,31(7N@P,(!3(01%!4!15!0!.30$1! "0,* %#*C( 0%$ + 2%42! 2 NMM, 3+ !0 433* ",0 OQ $,301 !",0! 31!@ !32!02! 1,(4!+21 EO(O= (PF 5!0! .30$1! "0,* *0% #! 1,2,.! ,02,0%!1= +@!32!02! %$(,0,*!2$+!51 !#11! 7P13!11%4!"0!!8!C 433*C2$57(!1%**! %2!(7!",0!31!@ +1203*!+22%,+? C+(71%15100%! ,32,+03'!0(2,+%11/3%0! 11.!20,*!2!0 5%2$!2,+%20%(!12$!1,(4!+2@20%611%12! 1!0!1,0.2%,+ ,+%82%,+%*!," (%#$2 E C,FC +(71!1 ," 2$! .,(7*!01 5!0! 00%! ,32 ,+ 03'!0 3(20"(!20!*!. 31%+#. OCGEOFCPCEQC
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
(6) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121. 8 1.!20,*!2!0 EN C PMM 8> NPC TR 8F@ 1%#+(1 5!0! 0!"!0!+! %+2!0+((7 2, 0!1% 3( 1,(4!+2 1%#+(1@ (20 .!0",0*+! (%/3% $0,*2,#0.$7B111.!20,*!207ECF+(71%1ECF51.!0",0*! ,+ 2!01JE C(11/3%27F712!*!/3%..! 5%2$.$,2, %, !007 !2!2,0 EF=C !2!2,0E I ,+%12%,+*, !F+ + J NU ,(3*+ EN@T <*= O@N 6RM **F@ ,0 1%+#(!C0712( *!130!*!+21= 2,! = !/3%..! 5%2$*,+,$0,*2! , (.$N0 %2%,+EM@TNMTPF5!0!31! ",02 + 2,! 2$!2=!/3%..! 5%2$*,+,$0,*2! 3 (.$N0 %2%,+EN@RQNUS F",01+ /*
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
(9) + 2$!/3!+$%+##!+2
(10) 5!0!*%6! 2,#!2$!0+ %11,(4! %+ 07 !#11! %$(,0,*!2$+!@ $%1 *%6230! 51 /3%'(7 . ! 2, 2$! %+%2%2,0. 1,(32%,+ + 2$! *%6230! 51 12%00! 2 0,,* 2!*.!0230! ",0 N $,30 2, !+130! ,*.(!2! ,+13*.2%,+ ," 2$! *,+,*!0@ $! .,(7*!0%82%,+ 51 /3!+$! 5%2$ M@N*,"!2$7(4%+7(!2$!02,2!0*%+2!+72%4!032$!+%3**!22$!1%11.!%!1+ 2$!+2$!1,(32%,+51,+!+202! 7"(,5,"0#,+@$!,+!+202! 1,(32%,+51 . ! 2,,( *!2$+,(2,.0!%.%22!2$!$!2!0,2!(!$!(%.,(7*!0@$!.,(7*!051. P .
(11) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121. 0! %11,(4! %+ %$(,0,*!2$+! + 0!.0!%.%22! ,+! *,0!= "%(2!0! = + 0%! 3+ !0$%#$433*@ 7.%(.0,! 30!",0 C1*.(!.0!.02%,+? O*#,"2$!.,(7*!051 %11,(4! %+N*," %$(,0,*!2$+!@O_,"2$%11,(32%,+ 51 . ! 2,OM_1,(32%,+,"O*#B%+ @N_,"N#%+! 51. ! 12$!%,+%8%+#1(2@$%11,(32%,+5112%00! ",0N*%+32!+ 2$!+1.,22! ,+. 2$! 20#!2 .(2! + (!"2 2, 0712((%8! ",0 PM *%+32!1@ $ C, *!130!*!+251(%02! #%+121 P!",0!0!,0 %+#2$!1.!203*@. . Q .
(12) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121. Synthesis Schemes:. $!*!N@7+2$!1%1,"131202!/@. $!*!O@7+2$!1%1,"2$!+2%1312%232! 131202!0@. $!*!P@7+2$!1%1,"+2%1312%232! 131202!1@ . R .
(13) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121. $!*! Q@ 7+2$!1%1 ," 131202! 2 2, 17+2$!1%8! *!22$!1%1 2(7121 ,+2%+%+#2$!.$!+,(#0,3.@ . $!*!R@7+2$!1%1,"2$!.C0,*,1312%232! ,*.,3+ 3@. . $!*!S@7+2$!1%1,"+2%1312%232! 131202!4@. $!*!T@7+2$!1%1,"+2%1312%232! 131202!5@ . S .
(14) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121. . . . . . %")& (%&#/,,). . . . %#30!N?%*!0!1,(4! N CE %$(,0,*!2$+!C O=PMM 8F1.!20@,0!2%,+ 51,1!04! ,+ %2%,+,"/2,P!/3%4(!+21,"/!4!+"2!0OQ$@ . . VM*%+EVQYF SM*%+EVNYF PM*%+EVMYF NM*%+ETSYF M*%+EMYF M % EM YF . . . .
(15) .
(16) . . . . . . . . %#30!O?%*!0!1,(4! N CE!+8!+!C S=PMM 8F1.!20,"2$!0!2%,+,"/ 5%2$P!/3%4(!+21,",*.,3+ 2@$!0!2%,++!! ! *,0!2%*!1,*.0! 2, 2$!0!2%,+%+ %$(,0,*!2$+!C O@ . . T .
(17) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121. C,2?. . . %#30!P? C,*111.!203*,"2$!$!2!0,2!(!$!(%.,(7*!017+2$!1%8! 5%2$ /@ + 2,.= 2$! 8,,*! %+ 0!#%,+ ," 2$! 1!(!2! .!' %1 1$,5+@ $! ,1!04! *,(!3(05!%#$2%1%+!6!((!+2#0!!*!+25%2$2$!2$!,0!2%((7(3(2! *,(!3(0 5!%#$2@ . . U .
(18) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121 2? . . . +. 5. . PTOM. QQSM N@OM. . . %#30!Q? E F20!,"$!2!0,2!(!$!(%.,(7*!05%2$/@ . . V .
(19) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121. &## !$!"(. . 51 .0!.0! ,0 %+# 2, 2$! .0!4%,31(7 0!.,02! .0,! 30!@O N C E$(,0,",0*C =PMM 8F?;E..*F]S@OUE2=
(20) ]N@U 8=O F=P@OMCP@PSE*=O F=O@VSE1= P F=O@SVE =
(21) ]N@N 8=O F=N@RNE 2=
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
(23) ]O@O 8=O F=S@RVE2=
(24) ]N@R 8= O F= P@TV E1= N F= P@PT C P@QP E*= O F= N@NR ..* E1= V F@ NPC E$(,0,",0*C =TR 8F?;E..*F]NPV@U=NPT@P=NMQ@P=TP@R=RR@R=OU@P..* . NM .
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
(26) ]O@R=N@M 8=O F=Q@QNE1=N F=. P@SRE. =
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
(28) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121. %#30!R?%+#(!0712(C071203230!,"2,+"%0*%+#2$!17+12!0!,$!*%1207@ NQTQQPS,+2%+12$!13..(!*!+2070712((,#0.$% 2",02$%1..!0@$!1! 2+! ,2%+! "0!!,"$0#!"0,*$!*0% #!0712((,#0.$%2!+20!@ +34>7 DKEF3>63F33@6EFDG5FGD7D78;@7?7@F8AD #67@F;8;53F;A@5A67 ?B;D;53>8AD?G>3 "'
(29) AD?G>3I7;9:F +7?B7D3FGD7
(30)
(31) $ .3H7>7@9F:
(32)
(33) M DKEF3>EKEF7? &A@A5>;@;5 *B3579DAGB 5 ,@;F57>>6;?7@E;A@E 3 M 4
(34)
(35) M 5 M -A>G?7
(36) M / 7@E;FK53>5G>3F76 4EADBF;A@5A788;5;7@F
(37)
(38)
(39) DKEF3>E;L7 +:7F3D3@978AD63F35A>>75F;A@ #@67JD3@97E )78>75F;A@E5A>>75F76 #@67B7@67@FD78>75F;A@E A?B>7F7@7EEFAF:7F3 N 4EADBF;A@5ADD75F;A@ &3J 3@6?;@ FD3@E?;EE;A@ )78;@7?7@F?7F:A6 3F3 D7EFD3;@FE B3D3?7F7DE !AA6@7EE A8 8;FA@ ;@3>);@6;57E0#E;9?3#1 );@6;57E3>>63F3 4EA>GF7EFDG5FGD7B3D3?7F7D JF;@5F;A@5A788;5;7@F %3D97EF6;88 B73=3@6:A>7. α
(40) N β
(41) N γ
(42) N . . &9 ?
(43)
(44) ??
(45)
(46)
(47) J
(48)
(49) J
(50)
(51) ??. FA N : =
(52) >
(53) 0);@F1 #@F79D3F;A@
(54)
(55) 3@6
(56)
(57) G>> ?3FD;J>73EF ECG3D7EA@ .
(58) )
(59)
(60) I)
(61) )
(62) I)
(63) .
(64)
(65)
(66) 3@6
(67) 7 M . NO .
(68) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121 +34>7 FA?;55AAD6;@3F7EJ
(69) 3@67CG;H3>7@F;EAFDAB;56;EB>357?7@FB3D3?7F7DEMJ
(70) 8AD ,7C;E678;@763EA@7F:;D6A8F:7FD357A8F:7ADF:A9A@3>;L76,;<F7@EAD 22222222222222222222222222222222222222222222222222222222222222222222222222222222 J K L ,7C 22222222222222222222222222222222222222222222222222222222222222222222222222222222 ' '
(71)
(72) '
(73)
(74)
(75) ' '
(76)
(77) '
(78) ' '
(79) '
(80) '
(81)
(82)
(83)
(84)
(85)
(86)
(87)
(88)
(89)
(90)
(91)
(92)
(93)
(94)
(95)
(96)
(97)
(98)
(99)
(100)
(101)
(102)
(103)
(104)
(105)
(106)
(107)
(108)
(109)
(110) +34>7 A@6>7@9F:E0M13@63@9>7E0N18AD 22222222222222222222222222222222222222222222222222222 ' .
(111)
(112) ' "'
(113) ' . ' " '
(114) ' . ' . '
(115) .
(116) ' . '
(117) . ' .
(118) '
(119) . ' . ' . ' . '
(120) . '
(121) .
(122) . . ".
(123)
(124)
(125)
(126) . . ".
(127)
(128)
(129)
(130) . . " .
(131)
(132)
(133)
(134) . NP .
(135) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121 " " " " " " " " " " " " " "
(136) " " " " " "
(137) " " " ' "' ' " ' '
(138) '
(139) ' ' ' ' ' " " " " " " ' ' ' " " " ' ' ' " ". . .
(140)
(141)
(142)
(143) . . .
(144)
(145)
(146)
(147) . .
(148)
(149)
(150)
(151) . .
(152)
(153)
(154) . .
(155)
(156)
(157)
(158) . .
(159)
(160)
(161)
(162)
(163)
(164)
(165) .
(166)
(167)
(168)
(169) .
(170)
(171)
(172)
(173) . .
(174)
(175)
(176)
(177)
(178)
(179)
(180)
(181)
(182) .
(183)
(184)
(185)
(186)
(187)
(188)
(189) .
(190)
(191)
(192)
(193)
(194)
(195)
(196)
(197)
(198)
(199)
(200)
(201)
(202)
(203)
(204)
(205)
(206)
(207) .
(208)
(209)
(210)
(211)
(212)
(213)
(214)
(215)
(216)
(217)
(218)
(219)
(220)
(221)
(222)
(223)
(224)
(225)
(226)
(227)
(228)
(229)
(230)
(231) . NQ .
(232) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121 " ' ' ' " " " ' ' ' " " " " " " " " " " " " " " " " " " '
(233) ' '
(234) ' " " " " " " " " " ' ' ' " " " " "
(235) "
(236) " " "
(237) " " " " " " " " ".
(238)
(239)
(240)
(241)
(242)
(243)
(244)
(245)
(246)
(247)
(248)
(249)
(250)
(251)
(252)
(253)
(254)
(255)
(256)
(257)
(258)
(259)
(260)
(261)
(262)
(263)
(264)
(265)
(266)
(267)
(268)
(269)
(270)
(271)
(272)
(273)
(274)
(275)
(276)
(277)
(278)
(279)
(280)
(281)
(282)
(283)
(284)
(285)
(286)
(287) . NR .
(288) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121 "
(289) " "
(290) " "
(291) '
(292) '
(293) '
(294)
(295) '
(296)
(297)
(298) '
(299) ' '
(300)
(301) '
(302)
(303)
(304)
(305) "
(306)
(307) "
(308) " "
(309)
(310) "
(311) " "
(312) " "
(313) ' '
(314) '
(315) ' 2222222222222222222222222222222222222222222222222222222222222 *K??7FDKFD3@E8AD?3F;A@EGE76FA97@7D3F77CG;H3>7@F3FA?E +34>7 @;EAFDAB;56;EB>357?7@FB3D3?7F7DEMJ
(316) 8AD +:73@;EAFDAB;5 6;EB>357?7@F835FAD7JBA@7@FF3=7EF:78AD? B0:3, . :=34, 1 222222222222222222222222222222222222222222222222222222222222222222222222222222 , , , , , , 222222222222222222222222222222222222222222222222222222222222222222222222222222 '
(317) '
(318) ' ' '
(319) '
(320) '
(321) '
(322) '
(323) '
(324)
(325)
(326)
(327)
(328)
(329)
(330)
(331)
(332)
(333)
(334)
(335) 222222222222222222222222222222222222222222222222222222222222222222222222222222 +34>7 "K6DA97@5AAD6;@3F7EJ
(336) 3@6;EAFDAB;56;EB>357?7@FB3D3?7F7DEMJ
(337) 8AD 22222222222222222222222222222222222222222222222222222222222222222222222222222222 J K L ,7C 22222222222222222222222222222222222222222222222222222222222222222222222222222222. NS .
(338) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121 "'
(339)
(340)
(341)
(342)
(343)
(344)
(345) " '
(346)
(347)
(348)
(349)
(350)
(351)
(352)
(353) "
(354) "
(355) "
(356) " "
(357)
(358) "
(359)
(360)
(361)
(362) "
(363) "
(364) "
(365) "
(366) " "
(367) " "
(368) " "
(369) "
(370) "
(371)
(372) " " " "
(373) "
(374)
(375) "
(376)
(377)
(378) "
(379)
(380) " 22222222222222222222222222222222222222222222222222222222222222222222222222222222 +34>7 +ADE;A@3@9>7E0N18AD 2222222222222222222222222222222222222222222222222222222222222222 '
(381) '
(382) '
(383) '
(384) '
(385)
(386) ' '
(387) ' ' '. ' '
(388) ' '
(389) '
(390)
(391) '
(392)
(393)
(394) '
(395) '
(396) ' . NT .
(397) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121 '
(398)
(399)
(400) '
(401)
(402) ' '
(403) ' ' '
(404) ' ' '
(405) ' ' ' ' '
(406) '
(407)
(408) '
(409) ' '
(410) '
(411) ' '
(412)
(413) ' '
(414) ' 2222222222222222222222222222222222222222222222222222222222222222 *K??7FDKFD3@E8AD?3F;A@EGE76FA97@7D3F77CG;H3>7@F3FA?E +34>7 "K6DA97@4A@6E8AD0M3@6N1 2222222222222222222222222222222222222222222222222222222222222222222222222222 ". 6 " 6". 6. " 2222222222222222222222222222222222222222222222222222222222222222222222222222 ' "'. '
(415) . ' " '. '
(416) . 2222222222222222222222222222222222222222222222222222222222222222222222222222 *K??7FDKFD3@E8AD?3F;A@EGE76FA97@7D3F77CG;H3>7@F3FA?E J KL . . . . NU .
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
(419) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121. E =]T@S 8=O F=N@SOE1=N F=N@MP..*E =]T@M 8=O F@ NPCE$(,0,",0*C = TR 8F?;E..*F]NPQ@R=UO@R=QR@S=ON@P..*@ . 7+2$!1%1 ," EN=Q=T1FCTCEEEFCPCEQC*!2$,67.$!+7(F((7(F,67F%7(,GO@O@NH$!.2COC!+! E1F?,131.!+1%,+," ESR@Q*#=O@TO**,(=N@R!/F%+OM* %!2$7(!2$!02M, 51 $,301=. ! (,$,(4EOMM*#=N@UO**,(=N!/F@$%11,(32%,+5112%00! 2M,",0P ! O*," 07=C %*!2$7(",0**% !2$!+2$!03 !1,(32%,+,+2%+%+#. 2$! QC*!2$,67%++*7( 0,*% ! %+ %$(,0,*!2$+! 51 . ! 0,.5%1! ,4!0 PM. *%+@$%11,(32%,+5112%00! ,4!0+%#$22%((((2$!(,$,(451,+13*! E7F@ $!1,(32%,+51/3!+$! 5%2$%!52!0+ %(32! 5%2$52!0@$%11,(32%,+51 !6202! 5%2$P6RM*!2$7(!22!@$!,0#+%(7!015!0!,*%+! = 0%! ,4!0 #Q + 2$! 1,(4!+2 51 0!*,4! 3+ !0 433*@ $%1 03 ! ,*.,3+ 51 $0,*2,#0.$! ,+1%(%5%2$2B$!6+!N?V2,,2%+2$!.30!=,(,30(!11=1,(% ,*.,3+ 1%+UUY7%!( @ N CE %$(,0,*!2$+!C O=PMM 8F?;E..*F]T@OUC T@PSE*=O F=S@UNCS@UUE*=O F=S@RNE =
(420) ]NR@V 8=N F=S@NPE 2=
(421) ]NR@V=S@M 8=N. F=R@VUE2=
(422) ]O@O 8=O F=Q@MPE. =
(423) ]S@N=N@Q 8=O F=P@TVE1=P F=P@OUE1=N F=O@ST. E =
(424) ]N@T 8=O F=N@TQCN@UPE*=O F=M@VOCN@MN..*E*=O F@NPCE$(,0,",0*C =TR 8F?;E..*F]NRV@O=NPQ@O=NPN@S=NOV@S=NOT@S=NOQ@O=NNP@V=UU@V=SV@N=RR@P= QP@R=ON@U..* . ON .
(425) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121. . %#30!S@%+#(!0712(C071203230!,"1@NQTQQPT,+2%+12$!13..(!*!+207 0712((,#0.$% 2",02$%1..!0@$!1! 2+!,2%+! "0!!,"$0#!"0,*$! *0% #!0712((,#0.$%2!+20!@ +34>7 DKEF3>63F33@6EFDG5FGD7D78;@7?7@F8AD #67@F;8;53F;A@5A67 ?B;D;53>8AD?G>3 AD?G>3I7;9:F +7?B7D3FGD7 .3H7>7@9F: DKEF3>EKEF7? *B3579DAGB ,@;F57>>6;?7@E;A@E -A>G?7 / 7@E;FK53>5G>3F76 4EADBF;A@5A788;5;7@F
(426)
(427)
(428) DKEF3>E;L7 +:7F3D3@978AD63F35A>>75F;A@ #@67JD3@97E )78>75F;A@E5A>>75F76 #@67B7@67@FD78>75F;A@E A?B>7F7@7EEFAF:7F3
(429) N 4EADBF;A@5ADD75F;A@ &3J 3@6?;@ FD3@E?;EE;A@ )78;@7?7@F?7F:A6 3F3 D7EFD3;@FE B3D3?7F7DE !AA6@7EE A8 8;FA@ ;@3>);@6;57E0#E;9?3#1 );@6;57E3>>63F3 JF;@5F;A@5A788;5;7@F. "
(430) '
(431)
(432) $. M &A@A5>;@;5 5 3 M 4 M 5
(433) M M. α
(434) N β
(435)
(436) N γ
(437) N . .
(438) &9 ?
(439)
(440) ??
(441)
(442) J
(443) J
(444)
(445)
(446) ??
(447) FA
(448) N : =
(449) >
(450)
(451) 0);@F
(452)
(453) 1 #@F79D3F;A@
(454)
(455) 3@6
(456) G>> ?3FD;J>73EF ECG3D7EA@
(457)
(458) .
(459) )
(460)
(461) I)
(462) )
(463)
(464) I)
(465)
(466)
(467) . OO .
(468) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121 %3D97EF6;88 B73=3@6:A>7
(469)
(470)
(471) 3@6
(472) 7 M +34>7 FA?;55AAD6;@3F7EJ
(473) 3@67CG;H3>7@F;EAFDAB;56;EB>357?7@FB3D3?7F7DEMJ
(474) 8AD ,7C;E678;@763EA@7F:;D6A8F:7FD357A8F:7ADF:A9A@3>;L76,;<F7@EAD 22222222222222222222222222222222222222222222222222222222222222222222222222222222 J K L ,7C 22222222222222222222222222222222222222222222222222222222222222222222222222222222 '
(475) '
(476)
(477)
(478)
(479)
(480)
(481)
(482)
(483)
(484)
(485)
(486)
(487)
(488)
(489)
(490)
(491)
(492)
(493)
(494)
(495)
(496)
(497)
(498) +34>7 A@6>7@9F:E0M13@63@9>7E0N18AD 22222222222222222222222222222222222222222222222222222 ' . ' . ' . ' . . . "
(499)
(500)
(501) "
(502)
(503)
(504) . "
(505)
(506)
(507) "
(508)
(509)
(510) .
(511) . ".
(512)
(513)
(514)
(515) . "
(516)
(517)
(518) .
(519) "
(520)
(521)
(522) . ".
(523)
(524)
(525)
(526) ".
(527)
(528)
(529)
(530) . "
(531)
(532)
(533) "
(534)
(535)
(536)
(537) . "
(538)
(539)
(540)
(541) .
(542) "
(543)
(544)
(545)
(546) . .
(547) . "
(548)
(549)
(550) . "
(551)
(552)
(553) . . OP .
(554) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121 " " " " " ' ' " " " " " " " " " " " " " " " " " " " " " " ' ' ' " " " ' ' " " ' " " " "
(555)
(556) " "
(557)
(558) "
(559)
(560) "
(561)
(562)
(563) " " " " ' .
(564)
(565)
(566)
(567)
(568)
(569)
(570)
(571)
(572)
(573)
(574)
(575)
(576)
(577)
(578)
(579)
(580)
(581)
(582)
(583)
(584)
(585)
(586)
(587)
(588)
(589)
(590)
(591)
(592)
(593)
(594)
(595)
(596)
(597)
(598)
(599)
(600)
(601)
(602)
(603)
(604)
(605)
(606) . OQ .
(607) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121 '
(608) " " " " ' "
(609) ' "
(610) " "
(611) ' "
(612) " "
(613) " "
(614) 2222222222222222222222222222222222222222222222222222222222222 *K??7FDKFD3@E8AD?3F;A@EGE76FA97@7D3F77CG;H3>7@F3FA?E +34>7 @;EAFDAB;56;EB>357?7@FB3D3?7F7DEMJ
(615) 8AD+:73@;EAFDAB;5 6;EB>357?7@F835FAD7JBA@7@FF3=7EF:78AD? B0:3, . :=34, 1 222222222222222222222222222222222222222222222222222222222222222222222222222222 , , , , , , 222222222222222222222222222222222222222222222222222222222222222222222222222222 '
(616) '
(617)
(618)
(619)
(620)
(621)
(622)
(623)
(624)
(625)
(626)
(627)
(628)
(629)
(630)
(631) +34>7 "K6DA97@5AAD6;@3F7EJ
(632) 3@6;EAFDAB;56;EB>357?7@FB3D3?7F7DEMJ
(633) 8AD 22222222222222222222222222222222222222222222222222222222222222222222222222222222 J K L ,7C 22222222222222222222222222222222222222222222222222222222222222222222222222222222 "
(634) "
(635) "
(636) " "
(637)
(638) "
(639)
(640) "
(641)
(642) " " "
(643)
(644) "
(645) "
(646) "
(647) "
(648)
(649) " "
(650) . OR .
(651) 3..,02%+# +", + !*%+#C.!+%+#%+#(,1%+#!22$!1%1",03+2%,+(!22$!1%12(7121 "
(652)
(653) "
(654) " "
(655) +34>7 +ADE;A@3@9>7E0N18AD 2222222222222222222222222222222222222222222222222222222222222222
(656)
(657)
(658)
(659)
(660) ' ' '
(661) '
(662) ' ' ' '
(663)
(664)
(665)
(666)
(667)
(668)
(669)
(670)
(671) '
(672) ' ' . '
(673)
(674)
(675) 2222222222222222222222222222222222222222222222222222222222222222 *K??7FDKFD3@E8AD?3F;A@EGE76FA97@7D3F77CG;H3>7@F3FA?E . . . . OS .
Documents relatifs
Effectuez chaque expression à l’aide de l’ordre correct
3 Relationship of the mean retention time (MRT) of fluids and small particles in the reticulorumen (RR) of various ruminant species classified as ‘cattle-type’ or ‘moose-type’
[r]
UVDE incises at a vari- ety of lesions, including the two major photoproducts, CPDs and 6-4 photoproducts (6-4PPs), AP sites, oxidative damage, base-base mismatches and small
[r]
Je retourne voir Gloria mais cette fois-ci elle reste vague dans ses réponses, que son mari n’en sait pas plus, bref.. Ce n’est pas vers eux que j’aurai mes réponses ce
L’espoir de tous ces êtres, méritent un grand respect, Tous ont voulus renaitre, dans un nouvel aspect, Saluons leurs essais, même si non couronnés, Des
As was the case elsewhere, several of the first female students and professors in Switzerland later became key figures in the struggle for political participation, gender