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7 7 1.2 (9<D=77 D9;ED87PEF 8 DEE:G7A7:EF<AABP7 A7;:7<P7 &.&1,#. *9.&I:TM%3+2 ".*5:1,*F % +"*+*9 ".*F#5#)%2.#&1$%% +*0#,&)%2 *1+%4*F + )%,.%'()4% 1*4"'#1+&4% I&F%+%, *, ".%.*5 4#,&''*$#),.&. <+'% F 1&0#+,F# &1,%F&,*.& %+"*'(I:#,+2 %)#.,)J 4#,&''*$#),., )&".%4#., "'&,%)&(IV) [16, 21, 24] %'%.#)%J(IV) [49], *9.&I:T,+2 1*4"'#1+ + 4*)*5#),&,)* 1**.5%)%.*F&))4 4-%4%)*&$%'*1+%4*4, 1*,*.J %4##, 8-1*)K%/:.&$%T 1**.5%)%.*F&))*J %4%)*/.:"" + F):,.%4*'#1:'2.)*J F*5*.*5)*J +F2I(T 4#Y5: &,*4*4 F*5*.*5& %4%)*/.:"" % *1+%4)4 &,*4*4 &I*,& (89P< 3). G#&1$%% *1+%4*F + 1*4"'#1+&4% 1$",+-[ 4 (C) 2 ] ( = Me, Et, Ph), [ 5 (EtC)] % 5*+- [e 4 (MeC) 2 ] ".*,#1&T, F 42/1%3 :+'*F%23 "*0,% + 1*'%0#+,F#))4% F3*5&4%. 7F,*.&4%.&9*, [16, 21, 24, 49] 9'*,&1Y# "*1&I&)*, 0,* *1+%4 )#.#&/%.:T, +* +F*9*5)4% )%,.%'&4%, 0,* +F%5#,#'(+,F:#, * )#*93*5%4*+,% &1,%F&$%% )%,.%'&. '' [M] [M] ' ' '' M = IV, e IV 9P< 3. *0#,&)%# *1+%4*F + )%,.%'()4% 1*4"'#1+&4% "'&,%)(IV) %.#)%2(IV). 8.% %+"*'(I*F&)%% *,)*+%,#'()* '&9%'()3 4#,&''*$#),.*F,,&1%3 1&1 F&)&5%J(IV) [50, 51],.*5%J(III) [17, 18], )%1#'((II) [37, 52] %'% "&''&5%J(II) [20].#&1$%2 ".*,#1&#, + *9.&I*F&)%#4 3#'&,)3 1*4"'#1+*F, F 1*,*.3 4-%4%)*&$%'*1+%4 1**.5%)%.*F&) 1 4#,&'': 5F:42 &,*4&4% &I*,&. ; 5&))*4 +':0&#.#&1$%T F*I4*Y)*.#&'%I*F&,( 5F:42 +"*+*9&4%: %+3*52 %I *1+%4& % )%,.%'()*/* 1*4"'#1+& 4#,&''& %'% %I )%,.%'& % *1+%4)*/* 1*4"'#1+&.?9& F&.%&),& ".%F*52, 1 *5)*4: %,*4: Y# ".*5:1,: (89P< 4). 8.#5"*'&/&#,+2, 0,* +)&0&'& ".*%+3*5%, *9.&I*F&)%# 1*4"'#1+& 4#,&''&, +*5#.Y&M#/* )%,.%' % *1+%4 F 5*+-"*'*Y#)%% 5.:/ 1 5.:/:, I&,#4 F):,.%+K#.)*# +*0#,&)%# ".*+,.&)+,F#))* +9'%Y#))3 *1+%4& % )%,.%'&; "*+'#5)%J &1,%F%.:#,+2 I& +0U, 1**.5%)&$%%. B&1%4 *9.&I*4, *, ".%.*5 4#,&''*$#),.& I&F%+%, +"*+*9 1**.5%)&$%% *9.&I:TM#/*+2 4-%4%)*&$%'*1+%4& % F*I4*Y)*+,( F+,.#0)*/* +%),#I& %I )%,.%'*F % *1+%4)3 1*4"'#1+*F 4#,&''*F. =.:/%4 F&Y)4 K&1,*.*4, F'%2TM%4 )& ".*,#1&)%#.#&1$%%, 2F'2#,+2 +,#"#)( *1%+'#)%2 4#,&''*$#),.&. ;&Y)*+,( 5&))*/* K&1,*.& )&/'25)* ".*2F'2#,+2 F +.&F)#)%%.#&1$%J +*0#,&)%2 *1+%4*F + )%,.%'&4% )& "'&,%)#(IV) [16, 24, 25] % "'&,%)#(II) [14, 15, 19].?1+%4 '#/1*.#&/%.:T, + )%,.%'()4% 1*4"'#1+&4% "'&,%)(IV), 5&F&2 ".*5:1,.#&1$%% +

8 8 "*0,% 1*'%0#+,F#))4% F3*5&4% 5&Y# ".% 1*4)&,)*J,#4"#.&,:.#, F,* F.#42 1&1 )& "'&,%)#(II) ".*,#1&)%# "*5*9)3.#&1$%J I&,.:5)#)* 5&Y# F 9*'## YU+,1%3 :+'*F%23. [M] M = V IV, h III, i II, Pd II [M] '' '' ' ' 9P< 4. *0#,&)%# *1+%4*F + )%,.%'&4% F ".%+:,+,F%% F&)&5%2(IV),.*5%2(III), )%1#'2(II) % '' [M] "&''&5%2(II). ' '' [M] ' ;.&9*,# [19] "*1&I&)*, 0,* &1,%F&$%2 &'%K&,%0#+1%3 % &.*4&,%0#+1%3 )%,.%'*F "'&,%)*J(II) )#5*+,&,*0)& 5'2 :+"#S)*/* ):1'#*K%'()*/* ".%+*#5%)#)%2 1#,*1+%4*F ' 2 C= (' 2 = Me 2, C 4 8 ) 1 )%,.%'()4 '%/&)5&4. %S( ".% %+"*'(I*F&)%% 5%&'1%'$%&)&4%5)3 1*4"'#1+*F 5*+-[(C 2 ) 2 (PPh 3 ) 2 ] 2+ ( = Me, Et) 9'% "*':0#) 3#'&,)# ".*5:1, 4*)*+*0#,&)%2, ".%0U4 5'2 ".*,#1&)%2.#&1$%% 9'& )#*93*5%4& 5*"*')%,#'()&2 ^'#1,.*K%'()&2 &1,%F&$%2 5%&'1%'$%&)&4%5& 1&,%*)&4% Ag + %'% Cu 2+, 1*,*.#, "* ".#5"*'*Y#)%T &F,*.*F, +F2IF&T,+2 + /.:""*J 2 (89P< 5) [19]. Ph 3 P Ph 3 P 2 (BF 4 ) 2 ' ' (BF 4 ) 2 Ph 3 P 2 Ag + or Cu 2+ Ph 3 P 2 2 ' ' 9P< 5. C&,&'%I%.:#4*# 1%+'*,&4% (T%+& +*0#,&)%# 1#,*1+%4*F + )%,.%'()4% 1*4"'#1+&4% "'&,%)(II). 8*I5)## +*0#,&)%# *1+%4*F + )%,.%'()4% '%/&)5&4% 9'*.&+".*+,.&)#)* )& )%,.%' C ( ^'#1,.*)*&1$#",*.)# /.:"" Ph, C 2 % C 2 C 2 Me). G#&1$%2 ".*,#1&'& ".% 40

9 9 50 ºC %/%'% 4%1.*F*')*F*4 *9':0#)%% + *9.&I*F&)%#4 4*)*5#),&,)* 1**.5%)%.*F&))3 4- %4%)*&$%'*1+%4*F + :4#.#))4% F3*5&4% (89P< 6) [14, 15]. 50 ºC and/or MW irradiation 2 ' ' ' ' ' ' ' ' ' ' 9P< 6. >)5:$%.*F&))*# 4%1.*F*')*F4 %I':0#)%#4 +*0#,&)%# 1#,*1+%4*F + )%,.%'()4% '%/&)5&4% F 1*4"'#1+&3 "'&,%)(II). G#I:'(,&, ^1+"#.%4#),*F %,#*.#,%0#+1%3.&+0U,*F "*IF*'%'% :+,&)*F%,( *+)*F)# 5F%Y:M%# +%'.&++4&,.%F&#4*J.#&1$%% +*0#,&)%2 [21, 53, 54]. *5)*J +,*.*), ".#F.&M#)%# :+1*.2#,+2 I& +0U, ^'#1,.*K%'()*J &1,%F&$%% )%,.%'&, )&".%4#., 4#,&''&4% F F+*1%3 +,#"#)23 *1%+'#)%2 ( IV [16, 25, 27], e IV [16, 25, 27, 49] % h III [17, 18]) %'% 4*M)4% ^'#1,.*)*&1$#",*.)4% I&4#+,%,#'24%,,&1%4% 1&1 "#.K,*.%.*F&))# &'1%' [55]. 5.:/*J +,*.*), ".%)$%"%&'()* %)4 +"*+*9*4 :+1*.#)%2 +*0#,&)%2 2F'2#,+2 :F#'%0#)%# ):1'#*K%'()*+,% *1+%4&. B#4 )# 4#)## %+"*'(I*F&)%# *1+%4*F + 9ó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e, Et, n Pr, n Bu a Co( 3 ) 2 ' 2 C= ' 2 = Me 2, C b [Co II ] [Co II ] c ' 2 C= d 2 2 C [Co II ] [Co II ] f e ' 3 [Co II ] [Co II ] ' ' 2 C= 2 9P< 7. %),#I &4%5%)*F, ".*4*,%.:#4J 1#,*1+%4&4% % )%,.&,*4 1*9&'(,&(II). C**9M&'*+( [31], 0,* )%,.%', +*5#.Y&M%# 5*)*.)# I&4#+,%,#'%, &4%)%.:T,+2 ".% 50 ºC F ".%+:,+,F%% 1#,*1+%4*F % )%,.&,& 1*9&'(,& (89P< 7, a). -*.#&1$%2 )# ".*,#1&'&, #+'% F.#&1$%*))*J +4#+% ".%+:,+,F*F&',*'(1* *5%) %I &1,%F%.:TM%3 &/#),*F 1#,*1+%4 %'% +*'( 1*9&'(,&(II). 8.#5"*'*Y%,#'()J 4#3&)%I4.#&1$%% %I*9.&YU) )& 89P9 7. 8#.F4 S&/*4 2F'2#,+2 1**.5%)&$%2 )%,.%'& 1 4#,&''*$#),.: (89P< 7, b), I&,#4.#&1$%2 ".*,#1&#, "* 5F:4 )&".&F'#)%24. *5)*J +,*.*), )%,.%', &1,%F%.*F&))J 1**.5%)&$%#J 1 1*9&'(,:(II), FI&%4*5#J+,F:#, + 1#,*1+%4*4 + *9.&I*F&)%#4 4-%4%)*&$%'1#,*1+%4)*/* 1*4"'#1+& 1*9&'(,&(II) (89P< 7, c). 5.:/*J +,*.*), )%,.%' ".#,#."#F&#, /%5.*'%I 5* 1&.9*)*F*J 1%+'*, % &44%&1& (89P< 7, d). D&,#4 ".*%+3*5%,.#&1$%2 ):1'#*K%'()*/* I&4#M#)%2 1#,*1+%4& )& &44%&1 + *9.&I*F&)%#4 &4%5%)*F*/* 1*4"'#1+& (89P< 7, e). D&1'T0%,#'()4

11 11 ^,&"*4 2F'2#,+2 5#1**.5%)&$%2 &4%5%)*F*/* '%/&)5& I& +0U, #/* ".*,*)%.*F&)%2 + *9.&I*F&)%#4 &4%5%)%#F*J +*'%, F"&5&TM#J F :+'*F%23.#&1$%% F *+&5*1 (89P< 7, f) [31]. 7)&'*/%0)&2.#&1$%2 F ".%+:,+,F%% )%1#'2(II) ".% 100 ºC, ".*,#1&#, 5&'(S# [33] (89P< 8).?9.&I:TM%#+2 &4%5%) (89P< 8, a).#&/%.:t, + 1**.5%)%.*F&))4% 1 4#,&''*$#),.: )%,.%'&4% + *9.&I*F&)%#4 3#'&,)3 1,3,5-,.%&I&"#),&5%#)*F3 1*4"'#1+*F )%1#'2 (89P< 8, b). = Me, Et, n Pr, i Pr n Bu, C 2 a i( 3 ) 2 Me 2 C= [i(en) 3 ]( 3 ) 2 3 en c i ( 3 ) 2 b i( 3 ) 2 Me 2 C= 2 C d P< 8. %),#I 1,3,5-,.%&I&"#),&5%#)*F3 1*4"'#1+*F )%1#'2(II) % &$%'&4%5*F. 8*':0#))# '%/&)5 4*/:, 9,( F 42/1%3 :+'*F%23 5#1**.5%)%.*F&) % F5#'#) F 0%+,*4 F%5# (89P< 8, c). 8.% 5#1**.5%)&$%% F ".%+:,+,F%% F*5,.%&I&"#),&5%#) ".#,#."#F&T, /%5.*'%I 5* &$%'&4%5*F (89P< 8, d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

12 12 +**,F#,+,F#))*) )%,.%' F ".%+:,+F%% F*5 :+"#S)* % F 42/1%3 :+'*F%23 ".#F.&M&T,+2 F 1&.9*1+&4%5 (89P< 9, a) [38]. 8.% %+"*'(I*F&)%%,*'(1* *5)*/* %I 1*4"*)#),*F 1&,&'%,%0#+1*J +%+,#4 1#,*1+%4& %'% 3'*.%5& $%)1&(II).#&1$%2 )# ".*,#1&#,. =#,&'()* 4#3&)%I4 5&))*J.#&1$%% )# %I:0&'+2, *5)&1* &F,*. ".#5"*'*Y%'%, 0,* )& "#.F*4 ^,&"# ".*%+3*5%, +*0#,&)%# *1+%4& + )%,.%'*4 F):,.% 1**.5%)&$%*))*J +K#. $%)1&(II) (89P< 9, b), I&,#4 "*':0%FS%J+2 4-%4%)*&$%'1#,*1+%4 ".#,#."#F&#, /%5.*'%I 5* &4%5& +.#/#)#.&$%#J *1+%4& (89P< 9, c). a = Alk, Ar ' 2 = Me 2, C 4 8, C 5 10 Zn 2 ' 2 C= 2 2 ' 2 C= [Zn II ] b [Zn II ] c 2 ' 2 C= [Zn II ] C' 2 9P< 9. 8.*4*,%.:#4J +%+,#4*J $%)1(II)-1#,*1+%4 /%5.*'%I )%,.%'*F. 8*I5)## :5&'*+( :,*0)%,( ".#5"*'&/&#4J 4#3&)%I4.#&1$%% /%5.*'%I& F ".%+:,+,F%% )%1#'2(II) [22]. \,&'*5%)%,.%' ".#,#."#F&#, /%5.*'%I 5* +**,F#,+,F:TM#/* &4%5& F ".%+:,+,F%% +*'#J )%1#'2(II) % ".*"&)-2-*)*1+%4&.?9.&I:#,+2 1*4"'#1+ )%1#'2(II) + 5F:42 1**.5%)%.*F&))4% &4%5&4% (9P< 10, a). >),#.4#5%&, 9' %5#),%K%$%.*F&), *) 2F'2#,+2 ".*5:1,*4 +*0#,&)%2 4 ^1F *1+%4& + 2 ^1F )%,.%'&, 1*,*.J,.%5#),&,)* 1**.5%)%.:#,+2 1 4#,&''*$#),.: (89P< 10, b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ºC) [23]. ; ".%+:,+,F%% +*'#J )%1#'2 % 1#,*1+%4& :5&U,+2 "*':0%,( K,&'*$%&)%) F +:M#+,F#))* 9*'## 42/1%3 :+'*F%23 ( ºC) [23] (89P< 11, c).

13 2 a i 2+ 4 Me 2 C= [i II ] 2+ 2CMe2 CMe 2 4 Me 2 C= i 2+ b i c Me 2 C= 2 3 CMe 2 CMe 2 2 9P< 10. X%5.*'%I K,&'*)%,.%'& % %5#),%K%$%.*F&))J %),#.4#5%&, / 1 = / / 2 / a i 2+ 4 Me 2 C= 1 1 2CMe2 CMe 2 i CMe 2 CMe i Me 2 C= c 1 i b P< *4*,%.:#4J *1+%4&4% +%),#I K,&'*$%&)%)*F. 7F,*.&4.&9*, [23] :5&'*+( F5#'%,( %),#.4#5%&, 5&))*J.#&1$%%, ".#5+,&F'2TM%J +*9*J 1*4"'#1+ )%1#'2 + 5F:42,.%5#),&,)4% '%/&)5&4%, "*':0#))4% +*0#,&)%#4 K,&'*5%)%,.%'& % 1#,*1+%4& F +**,)*S#)%% 1:2, &)&'*/%0)J *"%+&))*4: )& 89P9 10 (89P< 11, a), 1*,*.J ".#,#."#F&#, ".#F.&M#)%# F* K,&'*$%&)%)*FJ 1*4"'#1+ )%1#'2(II) F ".%+:,+,F%% 5*"*')%,#'()3 2 ^1F K,&'*5%)%,.%'& (89P< 11, b). >4,&1Y# :5&'*+( +%),#I%.*F&,( +F*9*5)# K,&'*$%&)%) F *,+:,+,F%# 4#,&''& %I K,&'*5%)%,.%'& ".% ".*4*,%.*F&)%%.#&1$%% 1#,*1+%4&4% [23].

14 (9<D=77 <IGED87PEF 8 DEE:G7A7:EF<AABP7 A7;:7<P7 -#+4*,.2 )&,*, 0,* *90)* &'(5*1+%4 % 1#,*1+%4 ".*2F'2T, +3*Y%# ):1'#*K%'()# +F*J+,F&, 1*)#0)4% ".*5:1,&4% 4#,&''*".*4*,%.:#4*/* +*0#,&)%2 &'(5*1+%4*F + )%,.%'&4% 2F'2T,+2 )# 4-%4%)*&$%'&'(5*1+%4. 6'* *9)&.:Y#)* [13, 43-45, 60-63], 0,* *9.&I:TM%#+2 1**.5%)%.*F&))# %4%) C()=C(=)' (c9p< 12, a) ".#,#."#F&T,.&+"&5 )& )%,.%' C % &4%5 'C 2 (c9p< 12, b % c). ; I&F%+%4*+,% *, :+'*F%J ".*F#5#)%2.#&1$%% :5&U,+2 "*':0%,( 1&1 )%,.%' 'C,,&1 % +**,F#,+F:TM%J &4%5 'C 2 F.#I:'(,&,# "*+'#5:TM#J 1&,&'%,%0#+1*J /%5.&,&$%% *9.&I:TM#/*+2 )%,.%'& (c9p< 12, d). ;"#.F# 5&))J ".*$#++ :5&'*+( )&9'T5&,( :0U)4 89XP (c9p< 13) [13]. 6'* *9)&.:Y#)*, 0,* ".*5:1, ".%+*#5%)#)%2 &'(5*1+%4*F 1 ".*"%*)%,.%'()*4: 1*4"'#1+: "'&,%)(IV) 1$",+-[ 4 (EtC) 2 ] (c9p< 13, A) )# :+,*J0%F % 5&Y# F 42/1%3 :+'*F%23 ".#,#."#F&T,.&+"&5 )& )%,.%' (c9p< 13, C) % 1&.9*1+&4%5)J 1*4"'#1+ "'&,%)(IV) (c9p< 13, B). [M] a ' ' [M] b ' [M] c [M] ' 2 [M] 2 d ' 2 2 9P< 12. ;I&%4*5#J+,F%# &'(5*1+%4*F + )%,.%'()4% 1*4"'#1+&4% % 5&'()#JS%J.&+"&5 4- %4%)*&$%'&'(5*1+%4*F. D& "*+'#5)%# "2,( '#, 4#,&''*".*4*,%.:#4&2 5#/%5.&,&$%2 &'(5*1+%4*F F ".%+:,+,F%% )%,.%'*F "*':0%'& S%.*1*#.&+".*+,.&)#)%# % 9'&.#&'%I*F&)& F 1&,&'%,%0#+1%3 F&.%&),&3 + %+"*'(I*F&)%#4 4#,&''*$#),.*F Pd II [61, 62], h I [44], In III [43], Cu II [45, 60], i II [60], Co II [60], Zn II [60], Fe II [60], Mn II [60] % Mo VI [63]. =&))#.#&1$%% )&S'% ".%4#)#)%# F 5F:3 )&".&F'#)%23: "*':0#)%# 1&.9*1+&4%5*F 'C 2 %I &'(5*1+%4*F 'C() (9P< 12, a d) % +%),#I 1&.9*1+&4%5*F C 2 %I )%,.%'*F C (9P< 12, a c).

15 15 [ IV ] ' ' = Me; Ph; PhC Me Me Me ' [ IV ] ' [ IV ] C B A 9P< 13. ;I&%4*5#J+,F%# &'(5*1+%4*F + ".*"%*)%,.%'()4 1*4"'#1+*4 "'&,%)(IV) %.&+"&5 *9.&I:TM#/*+2 %4%)&. C&,&'%I%.:#4J 4#,&''&4% ".*$#++ 5#/%5.&,&$%% &'(5*1+%4*F 'C() + "*':0#)%#4 )%,.%'*F 'C :5&'*+(.#&'%I*F&,( 9#I :0&+,%2 )%,.%'& C 1&1 F /*4*/#))*4 F&.%&),# ".% 1&,&'%I# 1*4"'#1+&4% e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ºC [66], + 3'*.1+%4&4% I& 9*'## 5'%,#'()*# F.#42 ( ) ".% 45 ºC [27]. G#&1$%% +*0#,&)%2 &4%5*1+%4*F + )%,.%'&4% %IF#+,) 1&1 5'2 %)#.,)*/* 4#,&''*$#),.& "'&,%)(IV) [27],,&1 % '&9%'()*/* $%)1&(II) [30, 47, 48]. B&1Y# %IF#+,)& "*5*9)&2.#&1$%2 F 9#I4#,&''()*4 F&.%&),# + "#.K,*.%.*F&))4% &'%K&,%0#+1%4% )%,.%'&4%,.#0( * 1*,*.3 "*J5U, )%Y# [55]. <5%)+,F#))4 ".%4#.*4 +*0#,&)%2 &4%5*1+%4& + )%,.%'*4, 1**.5%)%.*F&))4 1 "'&,%)#(IV), 9'& /#,#.*/#))&2.#&1$%2 4#Y5: &$#,*)%,.%'()4 1*4"'#1+*4 1$",+-[ 4 (MeC) 2 ] % 9#)I&4%5*1+%4*4 PhC( 2 )= ".% 56 ºC F,#0#)%# 27 0, 1*,*.&2 ".%F*5%'& 1 %4%)*1*4"'#1+: "'&,%)(IV), +*5#.Y&M#4: 5F& 4*)*5#),&,)* 1**.5%)%.*F&))3 4-%4%)*&$%'&4%5*1+%4)3 '%/&)5& (89P< 15) [27]. ;I&%4*5#J+,F%#

16 16 &4%5*1+%4*F + )%,.%'&4% %),#.#+)*,#4, 0,* ".%F*5%, 1 3,5-5%I&4#M#))4 1,2,4- *1+&5%&I*'&4 [30, 47, 48, 67] X 2 C 2 2 X = Me = Me, Et 1 / 2 = / Me/Me X = = Me 1 / 2 = / /Me / X X 1 1 9P< 14. *0#,&)%# K:)1$%*)&'%I%.*F&))3 *1+%4*F + )%,.%'()4% 1*4"'#1+&4% "'&,%)(IV). 2 Me Me 2 Ph 2 56 ºC; 27 h Ph Me Me Ph 9P< 15. >IF#+,)J ".%4#. +*0#,&)%2 &4%5*1+%4& + )%,.%'()4 1*4"'#1+*4 "'&,%)(IV).

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d) [68]. 9P< 16.?+)*F)# ":,% "*':0#)%2 1,2,4-*1+&5%&I*'*F. 4-7$%'&4%5*1+%4, 2F'2TM%#+2 %),#.4#5%&,&4% F.#&1$%% *9.&I*F&)%2.&++4&,.%F&#43 /#,#.*$%1'*F %I &4%5*1+%4*F % /&'*/#)&)/%5.%5*F %'% &)/%5.%5*F 1&.9*)*F3 1%+'*, (89P< 16, %I*9.&Y#)%# F.&41#, Y = ), 3*.*S* %I:0#) [83-85].?5)&1* 4-%4%)*&$%'&4%5*1+%4 (89P< 16, %I*9.&Y#)%# F.&41#, Y = ), ".#5"*'*Y%,#'()*, 2F'2TM%#+2 %),#.4#5%&,&4% F.#&1$%% *9.&I*F&)%2 1,2,4-*1+&5%&I*'*F %I &4%5*1+%4*F % )%,.%'*F,.&)## 5#,#1,%.*F&) )# 9'%.

18 18 %),#I 1,2,4-*1+&5%&I*'*F, *+)*F&))J )&.#&1$%% )%,.%'*F + &4%5*1+%4&4%, ".*,#1&#, F F#+(4& YU+,1%3 :+'*F%23 ( º) [86]. P+'*F%2.#&1$%% 4*/:, 9,( +:M#+,F#))* +42/0#) (5* ºC), #+'% ".*F*5%,( #U F ".%+:,+,F%% 3'*.%5& $%)1& % +%'()*J 1%+'*, [ %'% #-,*':*'+:'(K*1%+'*, (8BC)] [30, 47, 48]. 8*4%4* ^,*/*, %IF#+,#) ".%4#. &1,%F&$%% )%,.%'*F ":,U4 "*':0#)%2 %I )%3 )%,.%'%#F3 +*'#J [67]. ; ^,*4 +':0&#,.#&1$%2 ".*,#1&#, + *9.&I*F&)%#4 1,2,4-*1+&5%&I*'*F, % ".*4#Y:,*0)# )#+,&9%'()# %4%)%#F# +*'% :5&'*+( 5#,#1,%.*F&,(. 7F,*..&9*, [47] ".%4#)%'% +%+,#4: Zn 2 + 8BC 5'2 :+1*.#)%2 +*0#,&)%2 &4%5*1+%4*F + )%,.%'&4% % ".#5"*'*Y%'%, 0,* Zn II +"*+*9+,F:#, *,M#"'#)%T &44%&1& *, &4%5*1+%4&, *9.&I:#,+2 )%,.%'*1+%5, 1*,*.J I&,#4.#&/%.:#, + )%,.%'*4 1&1 1,3-5%"*'( (89P< 17, "). Zn II /PTSA 3 ' a b Zn II ' 2 [Zn] Zn 2 ; 4 d c ' 2 " ' 2 " [ 3 "] + ' ' = perfluorinated alkyl 9P< 17. G&)## ".#5"*'&/&#4# 4#3&)%I4 *9.&I*F&)%2 1,2,4-*1+&5%&I*'*F %I )%,.%'*F % &4%5*1+%4*F. 2 CF 3 CF F; CF 3 C 2 7F,*..&9*, [30] %I:0%'% +3*Y:T 1&,&'%,%0#+1:T +%+,#4: (Zn 2 + ) + "*4*M(T +"#1,.*+1*"%% AG 15 %, )#+4*,.2 )&,*, 0,* )% *5%) %I %),#.4#5%&,*F )# 9' F5#'#) F

19 19 0%+,*4 F%5#, ".#5'*Y%'% %)*J 4#3&)%I4 *9.&I*F&)%2 1,2,4-*1+&5%&I*'*F. %3,*01% I.#)%2, +*0#,&)%# &4%5*1+%4& + )%,.%'*4 ".*%+3*5%, F):,.% 1**.5%)&$%*))*J +K#. $%)1& + *9.&I*F&)%#4 9%5#),&,)*/* '%/&)5&, & 1%+'*,& )#*93*5%4& 5'2 5#1**.5%)&$%% *5)*/* %I ):1'#*K%'()3 $#),.*F *9.&I:TM#/*+2 %4%)*&$%'%.*F&))*/* &4%5*1+%4& (89P< 17, b). D&,#4 ".*%+3*5%, $%1'%I&$%2 "*':0#))*/* '%/&)5& F):,.% 1*4"'#1+& + F5#'#)%#4 *1+&5%&I*'& F +F*9*5)*4 F%5#. ;.&9*,# [67] 9'* %I:0#)* FI&%4*5#J+,F%# )%,.%'%#F3 +*'#J + )%,.%'&4%.?9.&I:TM%#+2 %4%)%#F# +*'% *9'&5&'% :4#.#))*J +,&9%'()*+,(T % ".#,#."#F&'% $%1'%I&$%T ".% "*FS#))3,#4"#.&,:.&3 + *9.&I*F&)%#4 1,2,4-*1+&5%&I*'& % +*'% &44*)%2 (89P< 17, c). ;.&9*,# [55] +%),#I%.*F&'% 4-%4%)*&$%'&4%5*1+%4 %+3*52 %I &4%5*1+%4*F % )%,.%'*F, +*5#.Y&M%3 +%'()# ^'#1,.*)*&1$#",*.)# /.:"" ("#.K,*.%.*F&))# &'1%'). 8*':0#))# %4%) )# ".#,#."#F&'% +&4*".*%IF*'()*J $%1'%I&$%%, *5)&1* 1,2,4-*1+&5%&I*' :5&'*+( "*':0%,(, F*I5#J+,F:2 )& %4%) CF 3 CF (c9p< 17, d). 1.7 U9I A<8;E>V9SE 7889GEF<A7> -& *+)*F&)%% &)&'%I& '%,#.&,:.)3 5&))3, 4 "*+,&F%'% "#.#5 +*9*J =9I 7889GEF<;I :9<D=77 A?D9ET7IAESE Q:78E9G7A9A7> <P7GED87PEF D A7;:7<P, DEE:G7A7:EF<AABP D Q<;7A9(II) 7 Q<;7A9(IV) 7 7?@7;I G<IA9CW79 Q:9F:<V9A7> Q:EG?D;EF 8E@9;<A7>. ;.&41&3 5&))*/* %++'#5*F&)%2 "'&)%.*F&'*+( )#,*'(1*.&+S%.%,( +"#1,. %IF#+,)3 4#,&''*".*4*,%.:#43.#&1$%J +*0#,&)%2 )%,.%'*F + ):1'#*K%'&4%, )* % 9*'## 5#,&'()* %I:0%,( 4#3&)%I4 *9.&I*F&)%2 1,2,4-*1+&5%&I*'*F, &,&1Y# +.&F)%,(.#&1$%*)):T +"*+*9)*+,( &4%5*1+%4*F % 1#,*1+%4*F. 8*4%4* ^,*/*, 4 "'&)%.*F&'% %++'#5*F&,( F*I4*Y)*+,( 5&'()#JS%3 3%4%0#+1%3 ".#F.&M#)%J "*':0#))3 ".*5:1,*F +*0#,&)%2, 0,* F)#+'* 9 5*"*')%,#'()J F1'&5 F :Y# %4#TM%#+2 I)&)%2 F 1**.5%)&$%*))*J % *./&)%0#+1*J 3%4%%.

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tC) 2 ] 1, 1$",+-[ 4 (PhC) 2 ] 2, 1$",+-[ 4 (Me 2 C) 2 ] 3 % &4%5*1+%4 MeC( 2 )= 4, PhC 2 C( 2 )= 5, PhC( 2 )= 6 ((78?AED 1). G#&1$%2 &4%5*1+%4*F *4"'#1+&4% 1 3 ".*,#1&#, 9+,.* (4#)## 0#4 I& 10 4%)) ".% 1*4)&,)*J,#4"#.&,:.# ".% +**,)*S#)%%.#&/#),*F 1:1 % 2:1 + *9.&I*F&)%#4 %4%)*1*4"'#1+*F 7 17 (89P< 18). *#5%)#)%2 1 % 2.#&/%.:T, + 1 ^1F &4%5*1+%4*F 5 % 6 (F* F+#3 F*I4*Y)3 1*49%)&$%23) + *9.&I*F&)%#4 ".*5:1,*F 4*)*+*0#,&)% (89P< 18, a) c ".#"&.&,%F)4% F3*5&4% 81 95% "*+'# *0%+,1% + "*4*M(T 1*'*)*0)*J 3.*4&,*/.&K%%. C*4"'#1+ 9 % )#+1*'(1* )#%5#),%K%$%.*F&))3 "*9*0)3 ".*5:1,*F %4#'% 9'%I1%# F.#4#)& :5#.Y%F&)%2, #/* )# :5&'*+( "*':0%,( F 0%+,*4 F%5#, "*^,*4: *) 9' *3&.&1,#.%I*F&) F +4#+% + 5&))4% ".*5:1,&4%.

21 Me 1 Me 21 Me Me Me 3 Me Me 2 6 (78?AED 1. ;9.&))# *9_#1, %++'#5*F&)% ' a 7 10 ' ' 2 b ' ' c ' Y 8E9G7A9A7> ' 0BEG (%) 7 Et C 2 Ph 81 8 Et Ph 95 9 Me 2 C 2 Ph 100 (AG) 10 Me 2 Ph Et M# Et C 2 Ph Et Ph Ph Ph Me 2 Me Me 2 C 2 Ph Me 2 Ph 85 9P< 18. %),#,%0#+1%# ".#F.&M#)%2 1*4"'#1+*F "'&,%)(IV).

22 22 *#5%)#)%2 1$",+-[ 4 (C){=C()C(Me) 2 }] ( = Et, Me 2 ), "*':0#))# ":,U4 FI&%4*5#J+,F%2 1*4"'#1+*F 1 % 3 c 1 ^1F &4%5*1+%4& 4,.&I'&/&T,+2 )& +%'%1&/#'# % )# 4*/:, 9,( *0%M#) + "*4*M(T 1*'*)*0)*J 3.*4&,*/.&K%%. -#+4*,.2 )& ^,*, *9.&I*F&)%# 5&))3 1*4"'#1+*F 9'* "*5,F#.Y5#)* 5&))4% ^'#1,.*+".#J-4&++-+"#1,.*4#,.%% F+*1*/*.&I.#S#)%2 (Z>--;G): 5'2 +*#5%)#)%2 + = Et *9)&.:Y#) +%/)&' [M ] + (F0%+'#)* ) % [M EtC + ] + (F0%+'#)* ), 5'2 +*#5%)#)%2 + = Me 2 *9)&.:Y#) +%/)&' [M ] + (F0%+'#)* ). 8.*5:1, 4*)*+*0#,&)%2 9#)I*)%,.%'()*/* 1*4"'#1+& 2 + &4%5*1+%4&4% 4 6 5#,#1,%.*F&) )# 9'% F+'#5+,F%# 1.&J)# )%I1*J.&+,F*.%4*+,% %+3*5)*/* 1*4"'#1+& F 9*'(S%)+,F# *./&)%0#+1%3.&+,F*.%,#'#J. -&".%4#., ".%9&F'#)%# F,#0#)%# 6 0.&+,F*.& &4%5*1+%4& 6 F )%,.*4#,&)# 1 %),#)+%F)* "#.#4#S%F&#4*J +:+"#)I%% 1*4"'#1+& 2 F )%,.*4#,&)# F +**,)*S#)%% 1:1 ".%F*5%'* 1 *9.&I*F&)%T ".*5:1,& 9%++*0#,&)%2 14 % %+3*5)*/* 1*4"'#1+& 2 F +**,)*S#)%% ~1:1. 8.% FI&%4*5#J+,F%% 1*4"'#1+*F *"*')%,#'()4 ^1F%F&'#),*4 +**,F#,+,F:TM#/* &4%5*1+%4& 9'% "*':0#) +**,F#,+,F:TM%# ".*5:1, 9%++*0#,&)%2 12, 13, 16 % 17 (89P< 18, ). =.:/%4 4#,*5*4 "*':0#)%2 ".*5:1,*F 9%++*0#,&)%2 2F'2#,+2.#&1$%2 1*4"'#1+*F ^1F &4%5*1+%4*F 4 6. #)## 0#4 I& 10 4%) ".% 1*4)&,)*J,#4"#.&,:.# *9.&I:T,+2 ".*5:1,.#&1$%% + ".#"&.&,%F)4% F3*5&4% 72 91% "*+'# 1*'*)*0)*J 3.*4&,*/.&K%% (89P< 18, b). G#&1$%2 9#)I*)%,.%'()*/* 1*4"'#1+& 2 + &'%K&,%0#+1%4% &4%5*1+%4&4% 4, 6 F )&%9*'## 0&+,* %+"*'(I:#43 *./&)%0#+1%3.&+,F*.%,#'23 (C 2 2, C 3, Me 2 C, Me 2, Me % Et), 5&Y# ".% %),#)+%F)*4 "#.#4#S%F&)%% % :'(,.&IF:1*F*4 5%+"#./%.*F&)%% +:+"#)I%%, ".%F*5%, 1 +4#+% )#%5#),%K%$%.*F&))3 ".*5:1,*F. ; Z>-- ;G +"#1,.&3 ".*5:1,& +*0#,&)%2 *9)&.:Y#)* )# 9'*, % F.#&1$%*))*J +4#+% 9' I&K%1+%.*F&) 9#)I*)%,.%'. ;I&%4*5#J+,F%2 4#Y5: &4%5*1+%4&4% 4 6 % +F*9*5)4% )%,.%'&4% EtC, PhC % Me 2 C F CD 2 2 % (D 3 ) 2 S ".% 1*4)&,)*J,#4"#.&,:.# )# )&9'T5&#,+2 5&Y# "* %+,#0#)%% 7 5. =&))# *", "*5,F#.Y5&T,, 0,* ):1'#*K%'()*# ".%+*#5%)#)%# &4%5*1+%4*F 1 )%,.%'&4 2F'2#,+2 ".*$#++*4, ".*4*,%.:#44 "'&,%)*J(IV). >,&1,.#&1$%2 +*0#,&)%2 &4%5*1+%4*F + )%,.%'()4% 1*4"'#1+&4% "'&,%)(IV) ".*,#1&#, F /*4*/#))3 :+'*F%23 4#)## 0#4 I& 10 4%) ".% 1*4)&,)*J,#4"#.&,:.#, F,* F.#42 1&1 +*0#,&)%# 1#,*1+%4*F + "*5*9)4% 1*4"'#1+&4% ".*,#1&#, I& 10 4%) '%S( ".% ºC [16]. +F2IF&#4 5&))#.&I'%0%2 F +1*.*+,%.#&1$%% + +9-^KK#1,*4 /.:"" 2, ".%F*52M%4 1 :F#'%0#)%T ):1'#*K%'()*+,% *1+%4)*J /.:"" =.

23 L<:<D;9:7<=7> PEAE- 7 Z78-#-7P7AE<=7<7GED87PAB DEPQ9D8EF Q<;7AB(IV) ;+# "*':0#))# %4%)*1*4"'#1+ "'&,%)(IV) 9'% *3&.&1,#.%I*F&) + "*4*M(T 1*4"'#1+& K%I%1*-3%4%0#+1%3 4#,*5*F &)&'%I&, 1*,*.J F1'T0&' F +#92 %)K.&1.&+):T +"#1,.*+1*"%T F *9'&+,% (>C); +"#1,.*+1*"%T AG 1 - % 13 +.&IF2I1*J *, ".*,*)*F (AG 1 - % AG 13 {}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

24 24 *9.&I*F&)%# F*5*.*5)*J +F2I% + *1+%4)4 &,*4*4 &I*,& (:78?AED 2), 0,* F.&Y&#,+2 F +4#M#)%% 0&+,*, 1*'#9&)%J )& ~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` 1**.5%)%.*F&))3 1 "'&,%)#(IV) )%,.%'*F (:78?AED 3), F,* F.#42 1&1 +"#1,.&3 ".*5:1,*F 4*)*+*0#,&)% '% *9)&.:Y#) "*'*+ +.#5)#J %),#)+%F)*+,% F *9'&+,% , 3&.&1,#.)# 5'2 F&'#),)3 1*'#9&)%J C`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~

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

26 26 +'&9*"*'():T *9'&+,( *,)*+%,#'()* "*5*9)*/* +%/)&'& F Z-%I*4#.&3, )# %4#TM%3 5&))*J F*5*.*5)*J +F2I% [16, 21, 24, 25, 27]. ; "*'*Y%,#'()*4.#Y%4# Z>--;G 5'2 +*#5%)#)%J 7 17 *1&I&'%+( 3&.&1,#.%+,%0)4% "%1% "+#F5*4*'#1:'2.)3 %*)*F [M + ] +, [M + a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º. G&++,*2)%2, )&3*52M%#+2 F 5%&"&I*)# (9) (13) Å, 2F'2T,+2 3&.&1,#.%+,%0)4% 5'2 +F2I#J IV [16, 21, 24, 89], & 5'%) +F2I#J 3&.&1,#.%+,%0)4% 5'2 +F2I#J %4%) [16, 21, 24, 81]. ;+# +F2I% (1) (1) 2F'2T,+2,%"%0)4% 5F*J)4% +F2I24%, %3 5'%) )&3*52,+2 F 5%&"&I*)# 1.277(5) 1.310(4) Å [16, 21, 24, 90]. F2I% C F *1+%4)*J 0&+,% 4*'#1:' %4#T, 5F*J)*J 3&.&1,#. [1.292(4) 1.305(2) Å] [16, 21, 24, 90], F,* F.#42 1&1 +F2I%? [1.331(8) 1.341(2) Å] % +F2I%? [1.4658(18) 1.496(7) Å] 2F'2T,+2,%"%0)4% *5%)&.)4% +F2I24% [90]. X.:"" 2 % Me 2 (F 1*4"'#1+&3 15, 16 a 2, 17 2Me 2 C % 17 2C 3 ) %4#T, &4%5)J 3&.&1,#., 0,* "*5,F#.Y5&#,+2 ".% &)&'%I# 5'%) +**,F#,+,F:TM%3 +F2I#J : 1.335(7) 1.361(8) Å 5'2 +F2I#J 2 % 1.325(8) 1.336(6) Å 5'2 +F2I#J Me 2 [90]. ; 8, 11, 13 2Me 2 C % 14 %4%)*&$%'%.*F&))J *1+%4 )&3*5%,+2 F 8-1*)K%/:.&$%% (:78?AED 5), F 1*,*.*J )&9'T5&#,+2 F*5*.*5)&2 +F2I( 4#Y5: &,*4*4 F*5*.*5& %4%)*/.:"" % *1+%4)4 &,*4*4 &I*,& (+**,F#,+,F:TM%#.&++,*2)%2 '#Y&, F 5%&"&I*)# 2.542(3) 2.574(2) Å, & :/' º). 8*5*9)# F*5*.*5)# +F2I%.&)## )&9'T5&'%+( 5'2 4*)*5#),&,)* 1**.5%)%.*F&))3 %4%)*&$%'%.*F&))3 *1+%4*F [16, 21, 24, 25, 49]. =.:/&2 F):,.%4*'#1:'2.)&2 F*5*.*5)&2 +F2I( )&9'T5&#,+2 4#Y5: &,*4*4 F*5*.*5& &4%5)*J /.:"" % *1+%4)4 &,*4*4 1%+'*.*5& [ Å, :/*' º]. -&".*,%F, F +,.:1,:.&3 15, 16 a 2, 17 2Me 2 C % 17 2C 3 '%/&)5 )&3*52,+2 F Z- K*.4# (:78?AED 6), % 5'2 )%3 )&9'T5&#,+2 '%S( *5)& F):,.%4*'#1:'2.)&2 F*5*.*5)&2 +F2I( 4#Y5: &,*4*4 F*5*.*5& &4%5)*J /.:"" % &,*4*4 1%+'*.*5& *1+%4)*J /.:"" [ Å, :/*' º].

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ºC F,#0#)%# +:,*1. -#+4*,.2 )& ^,*,.&)## +**9M&'*+(, 0,* 5'2 5#1**.5%)&$%% 3#'&,)3 K*+K%)*F % /#,#.*$%1'*F F 1*4"'#1+&3 "'&,%)(II) + :+"#3*4 9'% ".%4#)#) $%&)%5 M#'*0)3 4#,&''*F [95-97]. ; 5*"*')#)%# 1 ^,*4:, $%&)%5 )# %4#T, +%/)&'*F F +"#1,.&3 AG 1 -, 0,* 9'&/*".%2,+,F*F&'* 9 4*)%,*.%)/: ".#F.&M#)%J +F*9*5)3 %4%)*F. ; +**,F#,+,F%% + ^,%4, )&4 :5&'*+( 5#1**.5%)%.*F&,( %4%) %I 1*4"'#1+*F "'&,%)(IV) ":,U4 F*I5#J+,F%2 )&.&+,F*. 1*4"'#1+*F F (D 3 ) 2 S 6-1.&,)4 %I9,1*4 ac [95, 96]. =#1**.5%)&$%2 '%/&)5*F ".*%+3*5%'& F,#0#)%# )#+1*'(1%3 +#1:)5 ".% 1*4)&,)*J,#4"#.&,:.# + *9.&I*F&)%#4 +F*9*5)3 4-%4%)*&$%'%.*F&))3 &4%5*1+%4*F (89P< 19, a). *)%,*.%)/ ".#F.&M#)%J "*':0#))3 %4%)*F *+:M#+,F'U) + "*4*M(T +"#1,.*+1*"%% AG 1 - % 13. 6'* :+,&)*F'#)*, 0,* %4%) ".#,#."#F&T, ".#F.&M#)%2 "* 5F:4 )&".&F'#)%24: $%1'%I&$%2 F +**,F#,+,F:TM%J 1,2,4-*1+&5%&I*' %.&+"&5 )& %+3*5)# )%,.%' % &4%5*1+%4 (89P< 19, b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n 2 +"*+*9+,F:#, "*0,% 1*'%0#+,F#))*4:.&+"&5: %4%)*F )& %+3*5)# )%,.%' % &4%5*1+%4.

29 0.5 ' ' a ac a 2 [(C) 6 ] excess a ' 3 c 1 b ' ' x 1 x Y 8E9G7A9A7> ' x 1 x 2 19 Et Me Et C 2 Ph Et Ph Ph Ph Me 2 Me <0.03 ~ Me 2 C 2 Ph <0.03 ~ Me 2 Ph <0.03 ~0.04 9P< 19. =#1**.5%)&$%2 4-%4%)*&$%'&4%5*1+%4*F % %3 5&'()#JS%# ".#F.&M#)%2. -:4#.&$%2 +*#5%)#)%J % F3*5 1*)#0)3 ".*5:1,*F ".%F#5#) F,&9'%$#. =&))# AG 1 - "*1&IF&T,, 0,* +*#5%)#)% "*+'# 5#1**.5%)&$%% + "#.%*5*4 "*':.&+"&5& ~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o-c m-c + p-c ". (78?AED 7. "#1,. AG 1 - F#M#+,F& 21. >4%) '% *3&.&1,#.%I*F&),*'(1* + "*4*M(T AG 1 - %I-I& 1*.*,1*/* F.#4#)% +:M#+,F*F&)%2, F,* F.#42 1&1 +*#5%)#)% '% 5*"*')%,#'()* *3&.&1,#.%I*F&) + "*4*M(T AG 13 {} (:78?AED 8).

31 31 C 6 C 7 2 C 4 C 6 C 2 C 3 C 5 C 7 C 1 C 6 C 7 C8 C 8 C 1 C 4 C 5 [(C) 6 ] 2 C 2 C ". 0 (78?AED 8. "#1,. AG 13 C{}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tC) 2 ] 26, 5*+-[ 2 (EtC) 2 ] 27, 1$",+-[ 2 (PhC) 2 ] 28, 5*+-[ 2 (PhC) 2 ] 29, 1$",+-[ 2 (Me 2 C) 2 ] 30, 5*+-[ 2 (Me 2 C) 2 ] 31 % &4%5*1+%4 MeC( 2 )= 4, PhC( 2 )= 6 (:78?AED 9).

35 35 Me Me 26 Me 27 Me 4 Me Me 6 Me 2 Me Me 30 Me Me 31 Me Me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b; 89P< 22, b). ; +F*T *0#.#5(, 5%&'1%'$%&)&4%5)# 1*4"'#1+ 30 % 31.#&/%.:T, + 1 ^1F &4%5*1+%4*F 4 % 6 + *9.&I*F&)%#4 1&,%*))3 (32[] % 33[]) % )#J,.&'()3 (34 % 35) 3#'&,)3 1*4"'#1+*F +**,F#,+,F#))* (89P< 21, a; 89P< 22, a).

36 ' [32](), [33]() e ' 2 4, 6 36 ' ' [44]() 2, [45]() 2, [46]( 3 ) 2 [48]( 3 ) 2 (X) 2 ' 2 4, 6 = Me 2 = Et, Ph a b 26, 28, 30 c d = Me 2 = Et, Ph 2 ' 2 4, 6 2 Ag 3, 2 Ag ' = Ph f ' 2 ' 4, ' g 9P< 21. %),#,%0#+1%# ".#F.&M#)%2 1$",+-1*4"'#1+*F 26, 28, 30. ' ' ' (X) 2 34, 35 [49]() 2, [50]() 2, [51]( 3 ) 2 [54]( 3 ) 2 ' 2 4, 6 = Me 2 = Me 2 a c CMe Ag 3, ' 2 2 Ag b d 4, 6 = Et, Ph = Et, Ph 27, 29, 31 = Ph e ' 2 4, 6 ' f ' ' P< 22. %),#,%0#+1%# ".#F.&M#)%2 5*+-1*4"'#1+*F 27, 29, 31.

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42 $%# (C () ) (%) ( () (=C) "#$%& + (=C) %&%' $& (78?AED 11. >C +"#1,. 1*4"'#1+& 42. 8*'*+& b(c`) )# ".*2F'2#, (C () ) (%) 0 ( () ( C) (=C) "#$%& + (=C) %&%' 3600 $& (78?AED 12. >C +"#1,. 1*4"'#1+& [32](). >4##,+2 %),#)+%F)&2 "*'*+& b(c`). ; +"#1,.&3 AG 1 - ".*5:1,*F 9%++*0#,&)%2 [44]() 2 61, &,&1Y# 1*4"'#1+*F 34 % 35 9'* *9)&.:Y#)* "* *5)*4: )&9*.: +%/)&'*F, F,* F.#42 1&1 F +"#1,.&3 ".*5:1,*F 4*)*+*0#,&)%2 [32](), [33](), ".%+:,+,F*F&'* "* 5F& )&9*.& +%/)&'*F F +**,)*S#)%% 1:1 *, %4%)& % )%,.%'&. &.&1,#.)*J 0#.,*J )#3#'&,)3 ".*5:1,*F % F'2#,+2 )&'%0%# F +'&9*4 "*'# 5F:3 :S%.#))3 +%/)&'*F + %),#/.&'()4 +**,)*S#)%#4 1:2, *,)*+2M%3+2 1 &,*4&4 F*5*.*5& %4%)*/.:"" % &4%5)*J /.:"" 2 (:78?AED 13). ;,*

43 43 Y# F.#42 F +"#1,.&3 3#'&,)3 ".*5:1,*F F +'&9*4 "*'# )&9'T5&T,+2,.% :S%.#))3 +%/)&'& F +**,)*S#)%% 1:1:1 +.&I'%0)4% 3%4%0#+1%4% +5F%/&4% &,*4*F F*5*.*5& &4%5)*J /.:"" (:78?AED 14). o-c m-c + p-c Ph Ph C 2 C ". (78?AED 13. "#1,. AG 1 - F#M#+,F& 59. (C 3 ) 2 3 C (C 3 ) 2 C ". (78?AED 14. "#1,. AG 1 - F#M#+,F& 32. %/)&' &,*4*F F*5*.*5& &4%5)*J /.:"" F 3#'&,)3 1*4"'#1+& % 51 54, F $#'*4, +4#M#) *,)*+%,#'()* +%/)&'*F.&++4&,.%F&#43 &,*4*F F +**,F#,+,F:TM%3 )#3#'&,)3 ".*5:1,& F +'&9*# "*'#. ; +"#1,.&3 1*4"'#1+*F [33]() % 35 +%/)&' &,*4*F F*5*.*5& 5%4#,%'&4%)*/.:"" +4#M#) F 9*'## +%'()*# "*'# ()& ~ ) "* +.&F)#)%T +

44 44 +%/)&'&4% +**,F#,+,F:TM%3 &$#,&4%5*1+%4)3 ".*%IF*5)3 [32]() % 34. =&))*# )&9'T5#)%# 4*Y#, 9,( *9_2+)#)* ^1.&)%.:TM%4 ^KK#1,*4 K#)%'()*J /.:"". 8*5*9)*# 2F'#)%# ^1.&)%.*F&)%2 K#)%'()*J /.:""*J )&9'T5&#,+2,&1Y# % 5'2 1*4"'#1+*F 42 % 43, F +"#1,.&3 1*,*.3 +%/)&' )- % 3- +4#M#) F 9*'## +%'()*# "*'# "* +.&F)#)%T + +**,F#,+,F:TM%4% +%/)&'&4% F 1$",+-%I*4#.&3 38 % 39 +**,F#,+,F#))* ()& ~ '2 )$1)- ".*,*)*F % '2 3-1"-".*,*)*F). ; "*'*Y%,#'()*4.#Y%4# Z>--;G 5'2 %*))3 +*#5%)#)%J *1&I&'%+( 3&.&1,#.%+,%0)4% "%1% 1&,%*)*F [M ] + ([32] + % [33] + ), [M 2] 2+ ([44] 2+, [45] 2+, [49] 2+ % [50] 2+ ), [M 2 3 ] 2+ ([46] 2+ [48] 2+ % [51] 2+ [54] 2+ ) % K.&/4#),)3 %*)*F [M - 2] + ([44] +, [45] +, [49] + % [50] + ), [M ] + ([46] + [48] + % [51] + [54] + ). ='2 )#%*))3 1*4"'#1+*F % &.&1,#.%+,%0)4% *1&I&'%+( "%1%, +**,F#,+,F:TM%# "+#F5*4*'#1:'2.)4 %*)&4 [M + 4 ] +, [M + a] + % [M + K] +. 8*4%4* ^,*/*, F +"#1,.&3,&1Y# )&9'T5&'%+( K.&/4#),)# %*) [M ] +, [M 2 ] +, "*5*9)# K.&/4#),)# %*) 2F'2T,+2,%"%0)4% 5'2 3'*.%5)3 1*4"'#1+*F "'&,%)(II). G#I:'(,&, ^'#4#),)*/* &)&'%I& 5'2 F+#3 "*':0#))3 1*4"'#1+*F +*/'&+:T,+2 +.&+0U,)4% 5&))4% 5'2 ".#5"*'&/&#43 +,.:1,:.. *'#1:'2.)# +,.:1,:. 1*4"'#1+*F 34, 35, 37, 43, [45]() 2, [46](Tf) 2, [50]() 2, [54]( 3 ) 2, 55 % 59 9'% :+,&)*F'#) 4#,*5*4 G7 (:78?AD7 15 % 16). ;+# 1**.5%)&$%*))# "*'%^5. "*1&IF&T,,%"%0):T "'*+1*-1F&5.&,):T /#*4#,.%T 1*4"'#1+*F. ;+# :/' F*1.:/ 4#,&''*$#),.& "'&,%)(II) 9'%I1% 1 90º (I& %+1'T0#)%#4 :/'*F F 3#'&,)3 1*4"'#1+&3). ='%) +F2I#J,.&F)# (12) (7) Å,%"%0) 5'2 +F2I#J II [89]. 7 5'%) +F2I#J %4%) % *1+%4,.&F)#, +**,F#,+,F#))*, 1.972(2) 2.033(3) Å % (18) 2.020(7) Å, %4#T, I)&0#)%2, 3&.&1,#.)# 5'2 +F2I#J II %4%) % II *1+%4 [19, 90]. ='%) +F2I#J % :/' F %4%)*&$%'%.*F&))3 *1+%4&3 +*/'&+:T,+2 +.&)## "*':0#))4% I)&0#)%24% 5'2 +3*Y%3 %4%)*1*4"'#1+*F "'&,%)(II) [14, 15, 19]. ; 3#'&,)3 1*4"'#1+&3 34, 35, [45]() 2, [46](Tf) 2, [50]() 2, [54]( 3 ) 2 (:78?AED 15) :/' )&3*52,+2 F 5%&"&I*)# 77.07(7)º 79.63(9)º. ; +*#5%)#)%23 [46](Tf) 2, [54]( 3 ) 2 +F2I% C %4%) 2F'2T,+2,%"%0)4% 5F*J)4% +F2I24% +* I)&0#)%24% 5'%) 1.276(3) (17) Å [16, 21, 49, 90]. ;,* Y# F.#42, F 5%4#,%'$%&)&4%5)3 ".*%IF*5)3 34, 35, [45]() 2 % [50]() 2 5'%) +F2I#J C %4%) %4#T, I)&0#)% (3) 1.316(10) Å, & 5'%) +F2I#J C Me (11) 1.339(10) Å, 0,* +F%5#,#'(+,F:#, F "*'(I: ".*4#Y:,*0)*/* "*.251& %3 1.&,)*+,% F+'#5+,F%# +*".2Y#)%2 4#Y5: )%4%. >)*# +*".2Y#)%# 9'* *9)&.:Y#)* 4#Y5: +F2I24% C *1+%4 % C 2 [1.3132(16) 1.330(3) Å % 1.314(3) 1.333(4) Å +**,F#,+,F#))*]. F2I%? [1.3349(15) 1.363(10) Å] %? [1.4446(14) 1.472(8) Å] 2F'2T,+2,%"%0)4% *5%)&.)4% +F2I24% [90].

45 45 ; +*#5%)#)%23 [45]() 2, [46](Tf) 2, [50]() 2 *1+%4)J K.&/4#), ".% +F2I% C= %4##, 8-1*)K%/:.&$%T, & F 1*4"'#1+&3 34 % 35 Z-1*)K%/:.&$%T. ; 3#'&,)*4 1*4"'#1+# [54]( 3 ) 2 5F& %4%)*'%/&)5& %4#T,.&I'%0):T 8/Z-1*)K%/:.&$%T. ; 8-%I*4#.&3 %4##,+2 F):,.%4*'#1:'2.)&2 F*5*.*5)&2 +F2I( 4#Y5: *5)%4 %I &,*4*F F*5*.*5& /.:"" 2 % *1+%4)4 &,*4*4 1%+'*.*5& ( Å, :/*' º). ; +*#5%)#)%23 34 % 35, +*5#.Y&M%3 %4%)*'%/&)5 F Z-1*)K%/:.&$%%, F*5*.*5)&2 +F2I( %4##,+2 4#Y5: &,*4*4 F*5*.*5& /.:"" 2 % &,*4*4 ( 3.099(4) % 3.092(3) Å, :/*' 156.8º % 163.1º +**,F#,+,F#))*). ;):,.%4*'#1:'2.)3 F*5*.*5)3 +F2I#J F %4%)*'%/&)5#, %4#TM#4 Z-1*)K%/:.&$%T, F +,.:1,:.# [54]( 3 ) 2 *9)&.:Y#)* )# 9'* / 4 Me 2 45 () () / 2 Me 2 1 / (Tf) 2 54 ( 3 ) 2 Me 2 (78?AED 15. *'#1:'2.)# +,.:1,:. 3#'&,)3 1*4"'#1+*F.

46 46 5*+-6%+3#'&, [49] 2+ [54] 2+ %4#T, )#"'*+1*# +,.*#)%#. >+1&YU))&2 /#*4#,.%2 *9:+'*F'%F&#, +:M#+,F*F&)%# 5&))3 1*4"'#1+*F F F%5# *",%0#+1% &1,%F)3 7- % 9-K*.4.?9# K*.4 +*#5%)#)%J [49] 2+ [54] 2+ 9'% *9)&.:Y#) + "*4*M(T G7.&$#4%0#+1%3 1.%+,&''*F [50]() 2 % [54]( 3 ) 2. ; 1.%+,&''%0#+1%3.#SU,1&3 9'% *9)&.:Y#) *9& %I*4#.& (:78?AED 16). Ph Ph () 2 Me 2 Me 2 Ph Ph () 2 Me 2 Me 2 M-isomer P-isomer (78?AED 16. >I*4#.%2 F#M#+,F& [50]() 2. ; +*#5%)#)%23 37, 43, 55 % 59 (:78?AED 17), +*5#.Y&M%3 4*)*5#),&,)* 1**.5%)%.*F&))# %4%)*'%/&)5, +F2I% C %4%) % *1+%4 2F'2T,+2,%"%0)4% 5F*J)4% +F2I24%, 1.251(3) 1.289(6) % 1.280(6) 1.305(3) Å +**,F#,+,F#))* [16, 21, 49, 90]. ;,* Y# F.#42 +F2I% C 2 [1.330(7) 1.345(7) Å], C [1.342(3) 1.353(6) Å] % [1.450(2) 1.477(5) Å] 2F'2T,+2,%"%0)4% *5%)&.)4% +F2I24% [90]. ; +*#5%)#)%23 37 % 43 +F2I% C )%,.%' 2F'2T,+2,%"%0)4%,.*J)4% +F2I24% C`, 1.135(6) % 1.147(6) Å +**,F#,+,F#))* [100, 101].

47 / 4 Me Me (78?AED 17. *'#1:'2.)# +,.:1,:. 1*4"'#1+*F + 4*)*5#),&,)* 1**.5%)%.*F&))4% '%/&)5&4%. >4%)*&$%'%.*F&))# &4%5*1+%4 F )#3#'&,)3 1*4"'#1+&3 )&3*52,+2 F 8-1*)K%/:.&$%% % F 4*'#1:'2.)3 +,.:1,:.&3 *9)&.:Y%F&T,+2 F):,.%4*'#1:'2.)# F*5*.*5)# +F2I% 4#Y5: &,*4*4 F*5*.*5& %4%)*/.:"" % *1+%4)4 &,*4*4 &I*,& [ 2.578(6) 2.623(6) Å, :/*' º] % 4#Y5: *5)%4 %I &,*4*F F*5*.*5& /.:"" 2 % *1+%4)4 &,*4*4 1%+'*.*5& [ Å, :/*' º]. 3.8 M<DX@9A79 ;.&41&3 5&))*/*.&I5#'& )&4% 9'% %I:0#).#&1$%% ):1'#*K%'()*/* ".%+*#5%)#)%2 &4%5*1+%4*F 1 )%,.%'()4 '%/&)5&4 F 1*4"'#1+&3 "'&,%)(II). 6'* *9)&.:Y#)*, 0,* 5&))#.#&1$%% ".*,#1&T, + 9ó'(S%4% F3*5&4% % F 9*'## 42/1%3 :+'*F%23, 0#4 "*5*9)#.#&1$%% + 1#,*1+%4&4% % &'(5*1+%4&4%. G#&1$%*))&2 +"*+*9)*+,( "* *,)*S#)%T 1 ):1'#*K%'()*4: ".%+*#5%)#)%T &4%5*1+%4*F 1 )%,.%'&4, 1**.5%)%.*F&))4 1 "'&,%)#(II), :4#)(S&#,+2 F.25: 5%4#,%'$%&)&4%5 > 9#)I*)%,.%' > ".*"%*)%,.%'. C*4"'#1+ F 5*+-1*)K%/:.&$%% 2F'2T,+2