HAL Id: hal-02566995
https://hal.archives-ouvertes.fr/hal-02566995
Submitted on 7 May 2020
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.
Carboboration of Alkynes with
Cyclodextrin-Encapsulated N -Heterocyclic Carbene Copper Complexes
Zhonghang Wen, Yongmin Zhang, Sylvain Roland, Matthieu Sollogoub
To cite this version:
Zhonghang Wen, Yongmin Zhang, Sylvain Roland, Matthieu Sollogoub. Carboboration of Alkynes with Cyclodextrin-Encapsulated N -Heterocyclic Carbene Copper Complexes. European Journal of Organic Chemistry, Wiley-VCH Verlag, 2019, 2019 (15), pp.2682-2687. �10.1002/ejoc.201900246�.
�hal-02566995�
!"#$%$%#"&'%() %*) +,-.(/0) 1'&2) !.3,%4/5&#'(67(3"809,"&/4) !6 :/&/#%3.3,'3)!"#$/(/)!%88/#)!%;8,/5/0)
!"#$%"&$%'()$*+&,'-#$%./$'!"&$%*+&,'0123&/$'4#2&$5*6+&,'&$5'7&88"/)9'0#22#%#9:6+&,'
+&,;$<8/898'=&>/</)$'5)'?"/./)'7#2@A92&/>)'B74'?C40'DEFE*'0#>:#$$)'B$/3)></8@'G'?&.H9<'=I')8'7I'?9>/)*'J*'=2&A)'K9<</)9*'LMNNM'=&>/<'OP>&$A)Q' RS.&/2T'<123&/$I>#2&$5U<#>:#$$)S9$/3)></8)IV>*'.&88"/)9I<#22#%#9:U<#>:#$$)S9$/3)></8)IV>''
'
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
</./2&>' A#$5/8/#$<*' 8")' /$8>&.#2)A92&>' A&>:#:#>&8/#$' >)&A8/#$' Z/8"' 8)>./$&2' &2Y1$)<' V9$A8/#$&2/X)5' :1' &2Y12' "&2/5)<*' 2)5' 8#' )[#A1A2/A' 3/$12' :#>#$&8)'<H)A/)<'&<'8")'.&]#>'/<#.)>I'`#Z)3)>*'&$')$5#A1A2/A'O#QS/<#.)>'Z&<'&2<#'#:<)>3)5'/$'<#.)'A&<)<I'W"/<'/<#.)>'Z&<'$#8'H>)3/#9<21'
#:<)>3)5' &$5' /<' 9$)[H)A8)5' A#$</5)>/$%' 8")' ^A2&<</A&2^' .)A"&$/<.I' W")' 5/>)A8' %)$)>&8/#$' #V' :#>#$' V9$A8/#$&2/X)5' O#QS&2Y)$)<' :1' A&>:#:#>&8/#$'#V'&2Y1$)<'/<'9$H>)A)5)$8)5I'
>(&#%493&'%()
()'H>)3/#9<21'5)<A>/:)5'O>!.?Q?9?2'A#.H2)[)<'/$'Z"/A"'8")'A#HH)>O;Q'A)$8)>'/<'5))H21')$A&H<92&8)5'/$'8")'A&3/81'#V'&'H>#8)A8)5' A1A2#5)[8>/$'O!'#>'"S?\Q'OP/%9>)'aQIa'W")'A#HH)>'A)$8)>'/<'.&/$8&/$)5'/$'8")'A&3/81'/$'&'Z)22S5)V/$)5'H#</8/#$'8">#9%"'2/%&8/#$':1'&$'!S
")8)>#A1A2/A'A&>:)$)'OC`?Q'2/%&$5'Z"/A"'A#3&2)$821'A&H<'8")'H>/.&>1'>/.'#V'8")'?\I''
?&3/8&$5S:&<)5'&$5'#8")>')$A&H<92&8)5'.)8&2'A#.H2)[)<'#VV)>'/$8)>)<8/$%'#HH#>89$/8/)<'8#'A#$8>#2'<)2)A8/3/81'/$'.)8&2SA&8&21X)5'
>)&A8/#$<IE' O!!6>!.?Q?9?2*' 5)>/3)5' V>#.' :)$X12SH>#8)A8)5' !S?\' &<' A&3/8&$5*' Z&<' H>)3/#9<21' <"#Z$' 8#' A&8&21X)' 8")' V#>.&2'
"15>#:#>&8/#$'#V'8)>./$&2'&2Y1$)<'/$'8")'H>)<)$A)'#V'O_H/$QE'&$5'7)b`*'F)8#'%/3)'2/$)&>'O=Q'3/$12':#>#$'<H)A/)<'&<'8")'.&]#>'/<#.)><' O0A").)'a&QIJ'\9)'8#'8")'"/%"'<8)>/A'A#$<8>&/$8'/.H#<)5':1'8")'!S?\'A&3/81*'8")'>)%/#<)2)A8/3/81'/$'V&3#>'#V'8")'2/$)&>'/<#.)>'#:<)>3)5' Z/8"'O!!6>!.?Q?9?2'A#925'$#8':)')[H2&/$)5':1'8")'A2&<</A&2'^H&>&22)2^'&HH>#&A"'#V'8")'&2Y1$)'8#'8")'?9G_':#$5IM'W#'&AA#9$8'V#>'8")'
#:<)>3)5'>)%/#<)2)A8/3/81*'&$'&28)>$&8/3)'^H)>H)$5/A92&>^'&HH>#&A"'Z&<'H>#H#<)5'Z"/A"'Z&<'<9HH#>8)5':1'\PW'A&2A92&8/#$<'O0A").)' a&QIJ';$8)>)<8/$%21*'A"&$%/$%'8")'$&89>)c</X)'#V'8")'?\'V>#.'!S?\'8#'8")'2&>%)>'"S?\'Z&<'V#9$5'8#'/$59A)'&'<Z/8A"'/$'.)A"&$/<.'&$5'
>)%/#<)2)A8/3/81I'
'
@'A9#/)BC'4)H>)<)$8&8/#$<'#V'A1A2#5)[8>/$S!S")8)>#A1A2/A'A&>:)$)'A#HH)>O;Q'A#.H2)['O!!S>!.?Q?9?2T'O&Q'\)3)2#H)5'<8>9A89>)'<"#Z/$%'8")'!S?\'.&A>#A1A2)d'O:Q'FS
\/.)$</#$&2'</5)S3/)Z'#V'8")'A#.H2)[d'OAQ'0A").&8/A'>)H>)<)$8&8/#$'#V'8")'?\'A&3/81'Z/8"'8")')$A&H<92&8)5'A#HH)>O;Q'A)$8)>I'
`)>)/$'Z)'H>)<)$8'#9>'>)<928<'A#$A)>$/$%'8")'A&>:#:#>&8/#$'>)&A8/#$'A&8&21X)5':1'O!!6>!.?Q?9?2'O0A").)'a:QIF*e*L*D'W"/<'/$A295)<' /$3)<8/%&8/#$' #V' 8")' .)8"12' :#>12&8/#$' #V' &' <)>/)<' #V' 8)>./$&2' &2Y1$)<' &$5' )[&.H2)<' #V' /$8>&.#2)A92&>' A&>:#:#>&8/#$' >)&A8/#$<*' 8")' 2&88)>'%/3/$%'/$'<#.)'A&<)<'9$)[H)A8)5'>)<928<'/$'8)>.<'#V'>)%/#<)2)A8/3/81I''
O RO OR RO
O
O
O OR
RO OR
O O OR
RO OR O O O
RO O OR RO
O O
RO
RO
OR
OR N N
CuCl
(!-ICyD)CuCl (R = Bn)
(b)
(c) (a)
Cu Cl
D32/;/)BC'?#HH)>SA&8&21X)5':#>12&8/#$'#V'&2Y1$)<'Z/8"'?\SC`?S:&<)5'2/%&$5<T'O&Q'=>)3/#9<21'>)H#>8)5'V#>.&2'"15>#:#>&8/#$'&$5'H)>H)$5/A92&>'&HH>#&A"'#V'8")'
&2Y1$)'Z/8"'O!!S>!.?Q?9?2d'O:Q'?&>:#:#>&8/#$'>)&A8/#$<'5)<A>/:)5'/$'8")'H>)<)$8'<8951I'
E/09,&0)"(4)?'03900'%()
f' V)Z' )[&.H2)<' #V' &HH2/A&8/#$' #V' OC`?Q?9?2' A#.H2)[)<' /$' 8")' A&>:#:#>&8/#$' >)&A8/#$' #V' /$8)>$&2' #>' 8)>./$&2' &2Y1$)<' "&3)' :))$'
>)H#>8)5Ig*aN'W#' )[H2#>)' 8")' )VV/A/)$A1' &$5' >)%/#<)2)A8/3/81' #V' 8")' O_H/$QES.)5/&8)5' A&>:#:#>&8/#$' #V' &2Y1$)<' /$' 8")' A&3/81' #V' O!!6
>!.?Q?9?2*' Z)' V/><8' /$3)<8/%&8)5' 8")' .)8"12:#>&8/#$' #V' H")$12' &A)812)$)' &<' &' .#5)2' >)&A8/#$' O0A").)' E*' 4' h' ="QI' B$5)>' 8")'
#H8/./X)5'A#$5/8/#$<*'&'A#$3)></#$'#V'gei'Z&<'#:8&/$)5':1'9</$%'J'.#2'i'#V'O!!6>!.?Q?9?2'&$5'J')j9/3I'#V'?`F;I'W")'2/$)&>'O=Q'3/$12' :#>#$'/<#.)>'F"'Z&<'#:8&/$)5'Z/8"'"/%"'>)%/#<)2)A8/3/81'OkggcaQ'Z/8"'$#'5)8)A8&:2)'8>&A)'#V'8")':>&$A")5'OGQ'/<#.)>'/$'8")'A>95)'
>)&A8/#$'./[89>)'OW&:2)'a*')$8>1'aQI'W#'&AA)2)>&8)'8")'A#$3)></#$*'8")'>)&A8/#$'Z&<'>9$'&8'eN'l?I'fV8)>'EJ'"'#V'>)&A8/#$'&$5'<8&$5&>5' Z#>YS9H*'F"' Z&<' /<#2&8)5' /$' LJi' 1/)25I' \)A>)&</$%' 8")' 8).H)>&89>)' 8#' EN' l?' 2)5' 8#' 2#Z)>' A#$3)></#$' &$5' 1/)25' :98' 8")' "/%"'
>)%/#<)2)A8/3/81'/$'V&3#>'#V'8")'2/$)&>'/<#.)>'/<'.&/$8&/$)5'OW&:2)'a*')$8>1'EQI';$'A#$8>&<8*'Z/8"'&'2#Z)>'A&8&21<8'A"&>%)'#V'E'.#2i*'&'
$#8/A)&:2)'5>#H'/$'<)2)A8/3/81'Z&<'#:<)>3)5'OgecJ*'W&:2)'a*')$8>1'FQ*'&28"#9%"'8")'/<#2&8)5'1/)25'/<'<2/%"821'/.H>#3)5'OLDiQI' '
'
D32/;/)FC'?#HH)>SA&8&21X)5'.)8"12:#>&8/#$'#V'&2Y1$)<'Z/8"'8")'!S?\SC`?S:&<)5'2/%&$5'!!6>!.?I' H"$,/)BC'?#HH)>SA&8&21X)5'.)8"12:#>&8/#$'#V'&2Y1$)<I+&,''
7(&#.) +,-.(/)O4Q) ?#$3$'i+:,' -/)25'i'OFmIQ+:,' >&8/#)FcI+A,'
a' B")O="Q) ge' LJ' kggca'OF"TI"Q'
E+5,' B")O="Q) Lg' Ma' kggca'OF"TI"Q' F+),' B")O="Q) gF' LD' gecJ'OF"TI"Q'
J' B$)O$S7)S="Q) DL' eE' gJce'OF$TI$Q'
M' B3)O%S7)S="Q) gE' LN' gMcM'OF3TI3Q'
e' B4)O$Sb7)S="Q) eN' JJ' gacg'OF4TI4Q'
L' B/)O%Sb7)S="Q) eM' Jg' gLcF'OF/TI/Q'
D' B*)O&Sb7)S="Q) JL' EF' gDcE'OF*TI*Q'
g' BA)O$S?2S="Q) gg' Mg' gDcE'OFATIAQ'
aN' B2)O%S?2S="Q) gN' Jg' gecJ'OF2TI2Q'
aa' B')O&S?2S="Q) kgg' FD' ggca'OF'TI'Q'
R THF, MeOH
Cu Bpin
(Bpin)2, tBuOK (!-ICyD)CuCl cat.
R
H Bpin
Linear (L)
" (previous work)
R
« perpandicular » approach
Cu
vinyl copper intermediate
R Bpin
MeOH H R
Bpin
R
THF, R1X (Bpin)2, tBuOK (!-ICyD)CuCl cat.
R
R1 Bpin
(this work) or R
Bpin R1 (a)
(b)
(Z)-isomer (unexpected)
!
R
THF, 60 °C (Bpin)2, tBuOK (!-ICyD)CuCl (4 mol%)
R
H3C Bpin
Linear (L)
1a-q R
Bpin CH3 +
Branched (B) CH3I (4 equiv.)
2a-q 3a-q
aE' BJ)O$SPS="Q) DF' Me' ggca'OFJTIJQ'
aF' B-)O&SPS="Q) gN' MD' gecJ'OF-TI-Q'
aJ' B,)O$S?PFS="Q) DF' MN' gecJ'OF,TI,Q'
aM' B;)O%S?PFS="Q) ga' Ma' gMcM'OF;TI;Q'
ae' B()O&S?PFS="Q) kgg' JF' kggca'OF(TI(Q'
aL+),' B%'O_$b?`EQ) Dg' MJ' DLcaF'OF%TI%Q'
aD+V,' B")O="Q) DE' Me' DEcaD'OF"TI"Q'
+&,'aIF'Rj9/3I'#V'O_H/$QE'&$5''_9bn'Z)>)'9<)5*'>)&A8/#$'8/.)'EJ'"d'+:,'?#$3)></#$'#V'8")'&2Y1$)'&$5'C74'1/)25'5)8)>./$)5':1'a`'C74'&$&21</<'#V'8")'A>95)'
>)&A8/#$' ./[89>)' :1' A#.H&>/<#$' Z/8"' 8")' /$8)>$&2' >)V)>)$A)' Oa*F*MS8>/.)8"#[1:)$X)$)*' NIFF' )j9/3IQd' +A,'=cG' >&8/#' 5)8)>./$)5' :1'a`' C74' &$&21</<' #V' 8")' A>95)'
>)&A8/#$' ./[89>)d' +5,' 4)&A8/#$' H)>V#>.)5' &8' EN' l?d' +),' 4)&A8/#$' H)>V#>.)5' Z/8"' E' .#2i' #V' O!!6>!.?Q?9?2d' +V,' ?#$8>#2' )[H)>/.)$8' H)>V#>.)5' Z/8"' J' .#2i' #V' O>K#Q?9?2I'
B$5)>' 8")<)' #H8/./X)5' A#$5/8/#$<*' 8")' <A#H)' #V' 8")' .)8"12:#>&8/#$' >)&A8/#$' Z&<' /$3)<8/%&8)5' Z/8"' &' <)>/)<' #V' &>#.&8/A' 8)>./$&2'
&2Y1$)<'OB$6(Q'<9:<8/898)5':1'3&>/#9<')2)A8>#$'Z/8"5>&Z/$%'#>'5#$&8/$%'%>#9H<'&8'8")'&*'%*'#>'$'H#</8/#$<'#V'8")'H")$12'>/$%I';$'&22' 8")<)')[&.H2)<*'8")'2/$)&>'O=Q'/<#.)>'F'Z&<'A#$</<8)$821'#:8&/$)5'&<'8")'.&]#>'/<#.)>'Z/8"'<)2)A8/3/8/)<'>&$%/$%'V>#.'gacg'8#'kggca' O>&8/#'FcIQI' ;8' /<' Z#>8"' 8#' $#8)*' 8"&8' V#>' 8")' 2#Z)<8' <)2)A8/3/81*' #:<)>3)5' Z/8"'$Sb7)SH")$12' &A)812)$)' OW&:2)' a*' )$8>1' eQ*' 8")' 2/$)&>' /<#.)>'F'/<'<8/22'<8>#$%21'H>)5#./$&$8'OF4cI4'h'gacgQI'P9>8")>.#>)*'8")')2)A8>#$/A'H>#H)>8/)<'#V'8")'&>#.&8/A'<9:<8/89)$8'<)).'8#'"&3)'
$#'5/>)A8')VV)A8'#$'A#$3)></#$<'&$5'/<#2&8)5'1/)25<*'8")':)<8'>)<928<':)/$%'>)&A")5'Z/8"'H")$12&A)812)$)'OB"*'4'h'`*'LJiQ'&$5'%S .)8"12S<9:<8/898)5'<9:<8>&8)'B3'OLNiQ'OW&:2)'a*')$8>1'MQ*'Z")>)&<'BA'O4'h'$S?2Q'OW&:2)'a*')$8>1'gQ'&$5'B-'O4'h'&SPQ'OW&:2)'a*')$8>1' aFQ*'V#>'/$<8&$A)*'%&3)'3)>1'A2#<)'1/)25<'OMDSMgiQ'&$5'</./2&>'<)2)A8/3/8/)<I'09:<8/898/#$'&8'8")'&(')&'H#</8/#$'2)5'/$'<)3)>&2'A&<)<'OB**' B'*'B(Q'8#'&'5)A>)&<)'/$'1/)25<':98'Z/8"#98')VV)A8'#$'<)2)A8/3/81I'W")'.#<8'</%$/V/A&$8'5>#H'/$'<)2)A8/3/81'ODLcaFQ'Z&<'#:<)>3)5'Z/8"'B%' V#>' Z"/A"' 8")' &2Y1$)' /<' <9:<8/898)5' :1' &$' &2Y12' %>#9H' O4' h' ?`Eb_$*' W&:2)' a*' )$8>1' aLQI' f' A#$8>#2' )[H)>/.)$8' H)>V#>.)5' Z/8"' 8")' A2&<</A&2':92Y1'C`?'2/%&$5'>K#'Oa*FS:/<OE*eS5//<#H>#H12H")$12Q/./5&X#2SES12/5)$)Q'/$<8)&5'#V'8")'?\S:&<)5'C`?'2/%&$5'!!6>!.?*'2)5'8#'
&' </%$/V/A&$8' 5>#H' /$' <)2)A8/3/81' OF"cI"' h' DEcaDQ' OW&:2)' a*' )$8>1' aDQ*' 8"9<' 5).#$<8>&8/$%' 8")' /.H#>8&$A)' #V'!!6>!.?' <8>9A89>)' V#>' A#$8>#22/$%'<)2)A8/3/81I'W")'2#Z'<)$</8/3/81'8#'&2Y1$)')2)A8>#$/A'H>#H)>8/)<'#:<)>3)5'")>)'Z/8"'!!6>!.?'&<'2/%&$5'Z&<'&2>)&51'#:<)>3)5'/$' 8")'V#>.&2'"15>#:#>&8/#$'>)&A8/#$'A&8&21X)5':1'O!!6>!.?Q?9?2'&$5'Z/8"'#8")>':92Y1'!S&2Y12S<9:<8/898)5'OC`?Q?9?2'A#.H2)[)<IJ*M&'W#'
&AA#9$8'V#>'8"/<')VV)A8*'/8'Z&<'<9%%)<8)5'8"&8'A#HH)>G&2Y1$)'A##>5/$&8/#$'/<'8")'H>#59A8S5)8)>./$/$%'<8)HIaa'
P9>8")>.#>)*'8")'2#Z'>)&A8/#$'>&8)'#:<)>3)5'Z/8"'?`F;'&<'8")')2)A8>#H"/2)*'A#.H&>)5'Z/8"'7)b`'OH>)3/#9<'Z#>YQ*J'<9%%)<8<'8"&8'8")'
>)&A8/#$'#V'8")'?\S).:)55)5'3/$12':#>#$'A#HH)>'/$8)>.)5/&8)'Z/8"'8")'&2Y12'"&2/5)'./%"8':)'/.H#>8&$8'/$'8")'Y/$)8/A<'#V'8")'>)&A8/#$IaE' C)[8*' 8")' H#8)$8/&2' #V' O!!6>!.?Q?9?2' Z&<' )[&./$)5' /$' 8")' /$8>&.#2)A92&>' A#HH)>SA&8&21X)5' A&>:#:#>&8/#$' >)&A8/#$IF*aF'W"/<' A1A2/X&8/#$'>)&A8/#$'A&$'2)&5')/8")>'8#'A1A2/A'&2Y12:#>#$&8)<'#>'8#'&2Y)$12:#>#$&8)<'<8&>8/$%'V>#.'&2Y)$)<'#>'&2Y1$)<*'>)<H)A8/3)21I'_#8"'
<8>9A89>)<' &>)' >)2)3&$8' V#>' V9>8")>' <1$8")8/A' 8>&$<V#>.&8/#$<' &$5' &>)' 3)><&8/2)' /$8)>.)5/&8)<' V#>' #>%&$/A' <1$8")</<I' f' V)Z' A#HH)>S A&8&21X)5'/$8>&.#2)A92&>'A&>:#:#>&8/#$'>)&A8/#$<'"&3)':))$'5)<A>/:)5'V>#.':#8"'/$8)>$&2'&$5'8)>./$&2'&2Y1$)<IaJ'W")'>)&A8/#$*'/$/8/&221'
>)H#>8)5' Z/8"' H>#H&>%12' )8")><' :1' o/$p<' %>#9H' /$' ENaF*aJ&' Z&<' V#9$5' 8#' %/3)' )[#A1A2/A' &2Y)$12' :#>#$&8)<' 8">#9%"' /$8>&.#2)A92&>'
>)&A8/#$'#V'8")':#>#$'3/$12'A#HH)>'/$8)>.)5/&8)'Z/8"'8")'/$8)>$&2')2)A8>#H"/2)'OP/%9>)'EQI'' '
'
@'A9#/)FI';$8>&.#2)A92&>'A&>:#:#>&8/#$'>)&A8/#$I'0A").&8/A'>)H>)<)$8&8/#$'#V'8")'A1A2/X&8/#$'#V')2)A8>#H"/2)SA#$8&/$/$%'&2Y1$)<I'
b9>'H>)3/#9<'#:<)>3&8/#$<'/$'8")'V#>.&2'"15>#:#>&8/#$'>)&A8/#$'#V'&2Y1$)<'A&8&21X)5':1'O!!6>!.?Q?9?2*'<"#Z)5'8"&8'/$8)>$&2'&2Y1$)<'
>)&A8)5'.9A"'<2#Z)>'8"&$'8)>./$&2'&2Y1$)<'59)'8#'/.H#>8&$8'<8)>/A'/$8)>&A8/#$<'Z/8"'8")'?\'A&3/81IJ';$'8")'H>)<)$8'<8951*'Z)'V#A9<<)5'
#$'8")'A1A2/X&8/#$'#V'8)>./$&2'&2Y1$)<'V#>'Z"/A"'3)>1'V)Z')[&.H2)<'"&3)':))$'>)H#>8)5'/$'8")'2/8)>&89>)IaJA*5)
B</$%'</.H2)'"&2#%)$#&2Y12'A"&/$<'O$#$'&A8/3&8)5')2)A8>#H"/2)<Q'&<'/$8)>$&2')2)A8>#H"/2)<'Z&<'H>)3/#9<21'V#9$5'$#8'V&3#9>&:2)'V#>'8")' /$8>&.#2)A92&>'A&>:#:#>&8/#$'8#'8&Y)'H2&A)I'P#>'/$<8&$A)*'8")'>)&A8/#$'Z/8"'&'8)>./$&2'&2Y1$)'<9A"'&<'eS:>#.#SaS")[1$)'Z&<'>)H#>8)5' :1';8#p<'%>#9H'8#'%/3)'2#Z'1/)25<'ODiQ'#V'A1A2/X)5'A#.H#9$5'L"*':1'9</$%'?9?2cO&S8#2QF='&<'A&8&218/A'<1<8).'OW`P*'FN'l?QIaJA'0/./2&>21*' 8")'(&$%'&$5'!"&#p<'%>#9H'/$/8/&221'$#8/A)5'8"&8'8")'A1A2/X&8/#$'#V'/$8)>$&2'&A)812)$/A'/#5/5)<'<9A"'&<'eS/#5#SaSH")$12SaS")[1$)'5/5'
$#8'H>#A))5'Z/8"'?9?2cO*S_9QF='&<'A&8&21<8'OW`P*'>8QIaJ)'W")'A1A2/X&8/#$'#V'8"/<'/$8)>$&2'H")$12S<9:<8/898)5'/#5#'&2Y1$)'O4'h'="*'P/%9>)' EQ'"&<':))$'#H8/./X)5'8#'%/3)'8")')[H)A8)5'3/$12:#>#$&8)'/$'eJi'1/)25I'`#Z)3)>*'8")'&HH2/A&8/#$'#V'8")'<&.)'A&8&218/A'<1<8).'8#' 8)>./$&2'&2Y1$)<'Z&<'$#8'>)H#>8)5I''
Cu
Bpin Bpin
cyclization
exocyclic vinyl boronates
R R
E R CuI cat.
(Bpin)2
E
' '
D32/;/)IC';$8>&.#2)A92&>'A&>:#:#>&8/#$'#V'&2Y1$)<'A&8&21X)5':1'O!!6>!.?Q?9?2'#>'O>K#Q?9?2I'>K#'h'a*FS:/<OE*eS5//<#H>#H12H")$12Q/./5&X#2SES12/5)$)I' H"$,/)FC'M!!6>!.?Q?9?2SA&8&21X)5'/$8>&.#2)A92&>'A&>:#:#>&8/#$'#V'&2Y1$)<I+&,''
R$8>1' f2Y1$)' C`?' ?#$3$'i+&,' -/)25'i+:,' 4&8/#'LcN+A,'
a' O") !!6>!.?' kgg' MN' eNTJN'
E+5,' O") !!6>!.?' kgg' Jg' gJTe'
F' O") >K#) kgg' ea' JaTMg'
J' O$) !!6>!.?' kgg' JN' kggTa'
M' O3) !!6>!.?' kgg' Ma' kggTa'
e' O$) >K#) kgg' kgg' kggTa'
+&,'E'Rj9/3I'#V'O_H/$QE'&$5''_9bn'Z)>)'9<)5d'+:,'?#$3)></#$'#V'8")'&2Y1$)'5)8)>./$)5':1'a`'C74'&$&21</<'#V'8")'A>95)'>)&A8/#$'./[89>)':1'A#.H&>/<#$'Z/8"'8")' /$8)>$&2'>)V)>)$A)d'+:,';<#2&8)5'1/)25d'+A,'LcN'>&8/#'5)8)>./$)5':1'a`'C74'&$&21</<'#V'8")'A>95)'>)&A8/#$'./[89>)d'+5,'W")'<#298/#$'#V':&<)'O'_9bn'a'7'/$'W`PQ'Z&<'
<2#Z21'&55)5'#3)>'a'"I'
()'V/><8'/$3)<8/%&8)5'8")'A1A2/X&8/#$'#V'8")'</.H2)'/#5#&2Y12S<9:<8/898)5'8)>./$&2'&2Y1$)'O"'OeS/#5#SaS")[1$)*'0A").)'FQI'W")'>)&A8/#$'
#V'O"' /$' 8")' H>)<)$A)' #V' D' .#2' i' #V' O!!6>!.?Q?9?2' Z&<' V#9$5' 8#' %/3)' A1A2/X)5' 3/$12' :#>#$&8)<'L"cN"' /$' MN' i' /<#2&8)5' 1/)25I' W")'
>)&A8/#$'/<'<2#Z*'&$5'>)j9/>)<'&:#98'EJ'"'#V'")&8/$%'&8'eN'l?'/$'W`P'8#'%)8'#H8/./X)5'1/)25<I';$8)>)<8/$%21*'8")'>)&A8/#$'A#$</<8)$821'
%&3)*'/$'>)H)&8)5')[H)>/.)$8<*'&'>&8/#'#V'AI&I'eNTJN'#V'8")')[H)A8)5')[#A1A2/A'3/$12':#>#$&8)'L"'&$5'&$')$5#A1A2/A'</[S.).:)>)5'O#QS 3/$12':#>#$&8)'N")OW&:2)'E*'R$8>1'aQI''
W")'V#>.&8/#$'#V'L"'O&2>)&51'#:<)>3)5'/$'2#Z'1/)25'V>#.'eS:>#.#SaS")[1$)Q*aJA'/<')[H)A8)5'V>#.'^+,&^'A1A2/X&8/#$'#V'8")'/$8)>.)5/&8)' 2/$)&>'O=Q'A#HH)>'3/$12':#>#$&8)*'Z"/A"'/<')[H)A8)5'8#':)'8")'.&]#>'/<#.)>'/$'8")'V/><8'>)&A8/#$'<8)H'O0A").)'J&QI';$'A#$8>&<8*'8")' V#>.&8/#$' #V'N"' /<' 9$)[H)A8)5' &$5' 9$H>)A)5)$8)5I' W")' A1A2#")[12' :#>#$&8)'N"' V#>.&221' >)<928<' V>#.' &$' ^+*-&^' A1A2/X&8/#$' #V' 8")' 2/$)&>'O=Q'A#HH)>'3/$12':#>#$&8)I'f'>&5/A&2'.)A"&$/<.'./%"8':)'H>#H#<)5'V#>'/8<'V#>.&8/#$'&<'<"#Z$'/$'0A").)'J:I'W")'V#>.&8/#$'#V'
&$'&2Y12'>&5/A&2'V>#.'&A)812)$/A'"&2/5)'>)59A8/#$'Z/8"'A#$A#./8&$8'#[/5&8/#$'#V'&'A#HH)>O;QS_H/$'<H)A/)<'8#'A#HH)>O;;Q'Z&<'H>)3/#9<21' H>#H#<)5'V#>'8")'V#>.&8/#$'#V'L"IaJ)'`#Z)3)>*'8")'H>/.&>1'>&5/A&2'8"&8'.&1':)'%)$)>&8)5'V>#.'eS/#5#SaS")[1$)'O"*'/<'$#8')[H)A8)5'8#' H>#A))5'/$8#'&'eS+*-&'A1A2/X&8/#$'H>#A)<<'8#'%/3)'N"I'?#$<)j9)$821*'Z)'H>#H#<)5'")>)'8"&8'&$'/$8>&.#2)A92&>'>&5/A&2'A1A2/X&8/#$'8&Y)<' H2&A)'/$'8")'A&3/81'#V'8")'O!!6>!.?Q?9?2'A&8&21<8'V>#.'8")'A#HH)>'3/$12':#>#$&8)'/$8)>.)5/&8)I'W"/<'.)A"&$/<.'&22#Z<'V#>'>)%)$)>&8/#$'
#V' O!!6>!.?Q?9;' &<' A&8&21<8I' ;8' %#)<' 8">#9%"' &' A#HH)>O;;Q' /$8)>.)5/&8)' Z"#<)' V#>.&8/#$' A#925' :)' V&3#9>)5' :1' 8")' <8>#$%' )2)A8>#$' 5#$&8/$%'C`?'2/%&$5I'()'&2<#'#:<)>3)5*'8"&8'5)A>)&</$%'8")'A#$A)$8>&8/#$'#V''_9bn'/$'8")'.)5/9.':1'<2#Z'&55/8/#$'#3)>'a'"*'2)5'8#'
&'5>&.&8/A'5)A>)&<)'#V'8")'&.#9$8'#V'N")OW&:2)'E*'R$8>1'EQIaM'W"/<')VV)A8'#V''_9bn'A#$A)$8>&8/#$'#$'L"cN"'>&8/#'A#925'$#8':)'A2)&>21'
>&8/#$&2/X)5Iae'f$#8")>'H#<</:2)'H&8"Z&1'V#>'8")'V#>.&8/#$'#V'8")'</[S.).:)>)5'A1A2)'N"'/$3#23)<'O"Q#O#Q'/<#.)>/X&8/#$'#V'8")'./$#>' :>&$A")5'OGQ'3/$12'A#HH)>':#>#$&8)'/<#.)>'V#22#Z)5':1'A1A2/X&8/#$'O0A").)'JAQIaL'`#Z)3)>*'#9>'&88).H8<'8#'H>#.#8)'N"'V#>.&8/#$' 9$5)>'H"#8#A&8&218/A'A#$5/8/#$<'8#'V&3#>'/<#.)>/X&8/#$*aL'Z)>)'9$<9AA)<<V92*'8")'>&8/#'L"cN"'>).&/$/$%'9$A"&$%)5'O5&8&'$#8'<"#Z$QI' W#' 8")' :)<8' #V' #9>' Y$#Z2)5%)*' 8")' &HH2/A&8/#$' #V' A2&<</A&2' C`?' 2/%&$5<' <9A"' &<'>K#' /$' 8")' /$8>&.#2)A92&>' A#HH)>SA&8&21X)5' A&>:#:#>&8/#$' >)&A8/#$' #V' 8)>./$&2' &2Y1$)<' "&<' $#8' :))$' >)H#>8)5Ig*aN' W")>)V#>)*' 8")' A1A2/X&8/#$' #V'O"' Z&<' &2<#' /$3)<8/%&8)5' Z/8"' O>K#Q?9?2'&<'A&8&21<8I'W")'>)&A8/#$'Z&<'V#9$5'8#'%/3)'&'./[89>)'#V'A1A2/X)5'3/$12':#>#$&8)<'L"cN"'/$'eai'1/)25I'7#>)'/$8)>)<8/$%21*'&' L"cN"'>&8/#'#V'JaTMg'Z&<'#:8&/$)5*'<"#Z/$%'8"&8'8")'C`?'2/%&$5'>K#'$#8'#$21')VV/A/)$821'H>#.#8)<'A1A2/X&8/#$'#V'</.H2)'8)>./$&2'&2Y1$)<' :98'&2<#'V&3#><'8")'V#>.&8/#$'#V'8")'9$)[H)A8)5'</[S.).:)>)5'3/$12:#>#$&8)'N"I''
P/$&221*' :&<)5' #$' >)A)$8' >)<928<' <"#Z/$%' 8"&8' /$8>&.#2)A92&>' A&>:#:#>&8/#$' >)&A8/#$<' %&3)' /.H>#3)5' 1/)25<' Z/8"' H>#H&>%12' )8")>' 5)>/3&8/3)<*aJA'Z)'<895/)5'8")'A1A2/X&8/#$'#V'O$cO3'Z/8"'O!!6>!.?Q?9?2'#>'O>K#Q?9?2'&<'A&8&21<8<I';$'&22'A&<)<*'Z)'#:<)>3)5')[A29</3)21' 8")'V#>.&8/#$'#V'8")')[#A1A2/A'V/3)S.).:)>)5'3/$12':#>#$&8)<'L"'#>'L$*'Z/8"'$#'5)8)A8&:2)'8>&A)<'#V'</[S.).:)>)5')$5#A1A2/A'3/$12' :#>#$&8)'OW&:2)'E*')$8>/)<'JGeQI'
'
THF, 60 °C (Bpin)2, tBuOK (NHC)CuCl (8 mol%) I 4a
X O
4b: X = I 4c: X = Br
Bpin Bpin
O
Bpin
5a 6a-(Z)
5b NHC = !-ICyD or IPr
D32/;/)OC'=#<</:2)'.)A"&$/<.<'V#>'/$8>&.#2)A92&>'A&>:#:#>&8/#$'>)&A8/#$<'A&8&21X)5':1'O!!6>!.?Q?9?2T'O&Q'^?2&<</A&2^'+,&'A1A2/X&8/#$'2)&5/$%'8#'/<#.)>'L"d'O:Q'
=>#H#<)5'>&5/A&2'H&8"Z&1'/$3#23/$%'+*-&'A1A2/X&8/#$'8#'%)8'8")'9$)[H)A8)5'/<#.)>'N"d'OAQ';<#.)>/X&8/#$'#V'8")'O"QS:>&$A")5'/<#.)>'&$5'A1A2/X&8/#$'#V'8")'&<S V#>.)5'O#Q'/<#.)>'8#'%/3)'N"I'
!%(3,90'%(0)
()' "&3)' <"#Z$' ")>)' 8"&8' 8")'!S?\S:&<)5' C`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cA&3/81' /$8)>&A8/#$<'/$'8")'/$/8/&2'&2Y1$)'&HH>#&A"'&$5'/$'8")'>)&A8/#$'#V'&2Y12'"&2/5)<'Z/8"'8")')$A&H<92&8)5'3/$12':#>#$'A#HH)>'/$8)>.)5/&8)I';$'
&55/8/#$*' Z)' "&3)' 5).#$<8>&8)5' 8"&8' O!!6>!.?Q?9?2' A&8&21X)5' 8")' /$8>&.#2)A92&>' A&>:#:#>&8/#$' #V' A"&22)$%/$%' &2Y1$)<' <9:<8>&8)<'
<9A"' &<' </.H2)' &A)812)$/A' "&2/5)<' 8#' %/3)' A1A2/X)5' 3/$12' :#>#$' <H)A/)<' /$' .#5)>&8)' 1/)25<I' f$' 9$H>)A)5)$8)5' V#>.&2'+*-&S81H)' A1A2/X&8/#$'#V'&'A#HH)>'3/$12':#>#$&8)'/$8)>.)5/&8)'8#'%/3)'&'A1A2#")[)$12':#>#$&8)'Z&<'#:<)>3)5I'W"/<'/$8>/%9/$%'>)%/#<)2)A8/3/81'Z&<'
&2<#'#:<)>3)5'Z/8"'8")':92Y1'C`?'2/%&$5'>K#'<9%%)<8/$%'&$')VV)A8'#V'8")'C`?'2/%&$5'A&HH/$%'8")'A&3/81I'W")'.)A"&$/<.'>).&/$<'8#' :)')29A/5&8)5'&$5'<"#925':)'V9>8")>')[H2#>)5I''
758/#';/(&",)D/3&'%()
P/(/#",<)f22'>)&A8/#$<'Z)>)'H)>V#>.)5'9$5)>'&$'&>%#$'&8.#<H")>)'9</$%'Z)22S5>/)5'>)&A8/#$'V2&<YI'B$2)<<'<8&8)5'#8")>Z/<)*'>)&A8&$8<'Z)>)'H9>A"&<)5' V>#.' A#..)>A/&2' <#9>A)<' &$5' 9<)5' &<' >)A)/3)5' Z/8"#98' V9>8")>' H9>/V/A&8/#$I' f22' 8")' <#23)$8<' 9<)5' &<' >)&A8/#$' .)5/&' Z)>)' 5/<8/22)5I' ?#29.$' A">#.&8#%>&H"1'Z&<'H)>V#>.)5'Z/8"'</2/A&'%)2'OaNNGENN'.)<"QI'C74'<H)A8>&'Z)>)'>)A#>5)5'#$'&'_>9Y)>'FNN'7`X'#>'JNN'7`X*'9</$%'8")'</%$&2'#V'8")'
>)</59&2'<#23)$8'&<'&$'/$8)>$&2'>)V)>)$A)I'W")'"/%"S>)<#298/#$'.&<<'<H)A8>#<A#H1'O`470Q'Z&<'H)>V#>.)5'#$'&'_>9Y)>'./A>bWbP'<H)A8>#.)8)>*'9</$%' f%/2)$8'R0;So'o#Z'?#$A)$8>&8/#$'W9$/$%S7/['&<'>)V)>)$A)I'
D&"#&'(A)Q"&/#'",0)"(4)E/"A/(&0)
O!!6>!.?Q?9?2'Z&<'<1$8")</X)5'&AA#>5/$%'8#'#9>'H>)3/#9<21'H9:2/<")5'H>#A)59>)Ia&'f2Y1$)<'B%*aD'O$*ag'&$5'O3*EN)Z)>)'H>)H&>)5'&AA#>5/$%'8#'>)H#>8)5' H>#A)59>)<I'
D&"(4"#4)8#%3/49#/)*%#)&2/);/&2.,$%#"&'%()%*)",-.(/0)3"&",.R/4)$.)M!!6>!.?S!9!,)OH"$,/)BQC) (!-ICyD)CuI
(b)
Cu Bpin
Cu Bpin I
5a I
Linear (L)
« exo » cyclization (a)
CuI Bpin Linear (L) I
I
CuI Bpin
« endo » cyclization
CuII Bpin
H I
CuI
Bpin HI
6a + (!-ICyD)CuI (c)
Cu
(E)-Branched (B) isomer
Bpin I
(E) (Z) vinylcopper isomerization
Cu
Bpin I
6a (Z)-Branched
f$'#3)$S5>/)5'<A>)Z)5'89:)'Z&<'A"&>%)5'Z/8"'O!!6>!.?Q?9?2'ONINa'..#2*'EgIN'.%Q'&$5':/<OH/$&A#2&8#Q5/:#>#$'OO_H/$QE*'NIFN'..#2*'LMIE'.%QI'fV8)>' :)/$%'<)&2)5'Z/8"'&'<)H89.*'8")'89:)'Z&<'H9>%)5':1'F'3&A99.S&>%#$'A1A2)<I'W`P'ONIM'.oQ'Z&<'&55)5'&$5'8")'./[89>)'Z&<'<8/>>)5'V#>'M'./$'&8'EN'l?I'f'
<#298/#$'#V''_9bn'aIN'7'/$'W`P'ONIF'.oQ'Z&<'&55)5I'fV8)>'<8/>>/$%'V#>'FN'./$*'8")'&2Y1$)'ONIEF'..#2Q'Z&<'&55)5'O$)&8'#>'5/<<#23)5'/$'8")'./$/.&2'
&.#9$8'#V'W`P'/V'<#2/5Q'V#22#Z)5':1'7);'ONIga'..#2*'MeIL'µoQI'W")'89:)'Z&<'<)&2)5'Z/8"'&'<A>)Z'A&H'&$5'8")'./[89>)'Z&<'<8/>>)5'&8'eN'l?'V#>'EJ'"I'fV8)>' A##2/$%*'8")'A>95)'>)&A8/#$'./[89>)'Z&<'V/28)>)5'8">#9%"'&'<"#>8'H&5'#V'A)2/8)':1'>/$</$%'Z/8"'5/)8"12')8")>*'&$5'A#$A)$8>&8)5'9$5)>'3&A99.I'W")'A>95)'
>)</59)' Z&<' H9>/V/)5' :1' </2/A&' %)2' A">#.&8#%>&H"1' OA1A2#")[&$)c5/)8"12' )8")>QI' W")' A#$3)></#$' #V' 8")' &2Y1$)' &$5' C74' 1/)25' #V' 8")' H>#59A8' Z)>)' 5)8)>./$)5':1'a`'C74'&$&21</<'#V'8")'A>95)'>)&A8/#$'./[89>)':1'A#.H&>/<#$'Z/8"'8")'/$8)>$&2'>)V)>)$A)'Oa*F*MS8>/.)8"#[1:)$X)$)QI'W")'>)%/#<)2)A8/3/81'
#V'8")'>)&A8/#$'Z&<'5)8)>./$)5':1'a`'C74'&$&21</<'#V'8")'A>95)'>)&A8/#$'./[89>)I''
M"S6OTOTLTL6H/&#";/&2.,6F6MF682/(.,8#%86B6/(.,S6BTITF64'%5"$%#%,"(/)OF"QT'.V'h'NIM'OA1A2#")[&$)c5/)8"12')8")>*'aETaQI'a`'C74'OJNN'7`X*'?\?2FQT'$'h' LIMFGLIJL'O.*'E`Q*'LIFeGLIEe'O.*'F`Q*'MILe'O5*'/'h'NIg'`X*'a`Q*'EIJE'O5*'/'h'NIg'`X*'F`Q*'aIFE'O<*'aE`Q'HH.I'W")'C74'5&8&'&>)'/$'&%>)).)$8'Z/8"'8")' 2/8)>&89>)IEa'
M"S6OTOTLTL6H/&#";/&2.,6F6MF6#6&%,.,8#%86B6/(.,S6BTITF64'%5"$%#%,"(/)OF$QT'.V'h'NIFM'OA1A2#")[&$)c5/)8"12')8")>*'ENTaQI'a`'C74'OFNN'7`X*'?\?2FQT'$' h'LIJa'O5*'/'h'DIE'`X*'E`Q*'LIaF'O5*'/'h'DIN'`X*'E`Q*'MILJ'O<*'a`Q*'EIJN'O<*'F`Q*'EIFJ'O<*'F`Q*'aIFa'O<*'aE`Q'HH.I'W")'C74'5&8&'&>)'/$'&%>)).)$8'Z/8"'8")' 2/8)>&89>)IEE'
M"S6OTOTLTL6H/&#";/&2.,6F6UF6M$6&%,.,S8#%86B6/(6B6.,V6BTITF64'%5"$%#%6,"(/)OF3QT'.V' h' NIFM' OA1A2#")[&$)c5/)8"12' )8")>*' ENTaQI' a`' C74' OFNN' 7`X*'
?\?2FQT'$'h'LIFN'O5*'/'h'gIF'`X*'E`Q*'LIEa'O8*'/'h'LIM'`X*'a`Q*'LIaN'O5*'/'h'LIM'`X*'a`Q*'MILM'O5*'/'h'NID'`X*'a`Q*'EIJN'O5*'/'h'NID'`X*'F`Q*'EIFM'O<*'F`Q*' aIFE'O<*'aE`Q'HH.I'W")'C74'5&8&'&>)'/$'&%>)).)$8'Z/8"'8")'2/8)>&89>)IEa'
M"S6F6UF6MO6Q/&2%5.82/(.,S8#%86B6/(6B6.,V6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%#%,"(/)OF4QT) .V'h'NIJ'OA1A2#")[&$)c5/)8"12')8")>*'aNTaQI'a`'C74'OJNN' 7`X*'?\?2FQT'$'h'LIJL'O5*'/'h'gIN'`X*'E`Q*'eIDM'O5*'/'h'gIN'`X*'E`Q*'MILN'O5*'/'h'NIg'`X*'a`Q*'FIDa'O<*'F`Q*'EIFg'O5*'K'h'NIg'`X*'F`Q*'aIFa'O<*'aE`Q'HH.I' W")'C74'5&8&'&>)'/$'&%>)).)$8'Z/8"'8")'2/8)>&89>)IEa'
M"S6F6UF6MI6Q/&2%5.82/(.,S8#%86B6/(6B6.,V6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%#%,"(/)OF/QT) .V'h'NIJ'OA1A2#")[&$)c5/)8"12')8")>*'aNTaQI'a`'C74'OFNN' 7`X*'?\?2FQT'$'h'LIEE'O5*'/'h'LIg'`X*'a`Q*'LIaJGLINa'O.*'E`Q*'eIDF'O555*'/'h'DIa*'EIM*'NID'`X*'a`Q*'MILe'O5*'/'h'NID'`X*'a`Q*'FIDa'O<*'F`Q*'EIJN'O5*'/'h'NID'
`X*'F`Q*'aIFE'O<*'aE`Q'HH.I'aF?'C74'OLM'7`X*'?\?2FQT'$'h'aMgIMD*'aMLIDN*'aJMIMM*'aEgIag*'aaDIMM*'aaFILe*'aaaIMF*'DFIaa*'MMIFL*'EMINJ*'ENIFF'HH.I'
`470'OR0;*'./A>#'WbPQ'%c0T'A&2A5'V#>'?ae`EF_C&bF'+7mC&,m'EgLIaeFM*'V#9$5'EgLIaeFMI'
M"S6F6UF6MF6Q/&2%5.82/(.,S8#%86B6/(6B6.,SV6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%#%,"(/)OF*QT'.V'h'NIJ'OA1A2#")[&$)c5/)8"12')8")>*'aNTaQI'a`'C74'OJNN' 7`X*'?\?2FQT'$'h'LIEg'G'LIEN'O.*'a`Q*'LIaD'O55*'/'h'LIJ*'aIg'`X*'a`Q*'eIgLG'eIDe'O.*'a`Q*'MIJa'Oj*'/'h'aIN'`X*'a`Q*'FIDN'O<*'F`Q*'EIFJ'O5*'/'h'aIN'`X*'F`Q*' aIFN'O<*'aE`Q'HH.I'W")'C74'5&8&'&>)'/$'&%>)).)$8'Z/8"'8")'2/8)>&89>)IEa'
M"S6F6UF6MO6!2,%#%82/(.,S8#%86B6/(6B6.,V6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%#%,"(/' OFAQT'.V' h' NIJM' OA1A2#")[&$)c5/)8"12' )8")>*' aETaQI' a`' C74' OJNN' 7`X*'?\?2FQT'$'h'LIJE'O5*'/'h'DID'`X*'E`Q*'LIED'O5*'/'h'DID'`X*'E`Q*'MILF'O5*'/'h'NIg'`X*'a`Q*'EIFD'O5*'/'h'NIg'`X*'F`Q*'aIFa'O<*'aE`Q'HH.I'aF?'C74'OaNN' 7`X*'?\?2FQT'$'h'aMeIJM*'aJEIFJ*'aFFIga*'aEDIJE*'aELIEL*'DFIEa*'EMINF*'ENIaF'HH.I'`470'OR0;*'./A>bWbPQ'%c0T'A&2A5'V#>'?aM`EN_?2C&bE'+7mC&,m' FNaIaaJN*'V#9$5'FNaIaaJgI'
M"S6F6UF6MI6!2,%#%82/(.,S8#%86B6/(6B6.,V6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%#%,"(/' OF2QT'.V' h' NIJM' OA1A2#")[&$)c5/)8"12' )8")>*' aETaQI' a`' C74' OFNN' 7`X*'?\?2FQT'$'h'LIMNGLIJF'O.*'a`Q*'LIFgGLIFF'O.*'a`Q*'LIEeGLIEE'O.*'E`Q*'MILM'O5*'/'h'NID'`X*'a`Q*'EIFD'O5*'/'h'NID'`X*'F`Q*'aIFa'O<*'aE`Q'HH.I'W")' C74'5&8&'&>)'/$'&%>)).)$8'Z/8"'8")'2/8)>&89>)IEa'
M"S6F6UF6MF6!2,%#%82/(.,S8#%86B6/(6B6.,V6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%#%,"(/' OF'QT'.V' h' NIJM' +A1A2#")[&$)c5/)8"12' )8")>' OaETaQ,I' a`' C74' OJNN' 7`X*'?\?2FQT'$'h'LIFMGLIFa'O.*'a`Q*'LIEaGLIae'O.*'F`Q*'MIFJ'Oj*'/'h'aIN'`X*'a`Q*'EIFF'O5*'/'h'aIa'`X*'F`Q*'aIFE'O<*'aE`Q'HH.I'aF?'C74'OaNN'7`X*'
?\?2FQT'$'h'aMDIDF*'aJMILN*'aFaINe*'aEgIeD*'aEgIEL*'aEDIEJ*'aEeILJ*'DFIaD*'EMIND*'EEIEF'HH.I'`470'OR0;*'./A>bWbPQ'%c0T'A&2A5'V#>'?aM`EN_?2C&bE'
+7mC&,m'FNaIaaJN*'V#9$5'FNaIaaFJI'
M"S6F6UF6MO6@,9%#%82/(.,S8#%86B6/(6B6.,V6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%#%,"(/' OFJQT'.V' h' NIJM' OA1A2#")[&$)c5/)8"12' )8")>*' aETaQI' a`' C74' OJNN' 7`X*'?\?2FQT'$'h'LIMNGLIJF'O.*'E`Q*'LINFGeIge'O.*'E`Q*'MILN'O5*'/'h'NIL'`X*'a`Q*'EIFD'O5*'/'h'NIg'`X*'F`Q*'aIFa'O<*'aE`Q'HH.I'W")'C74'5&8&'&>)'/$'
&%>)).)$8'Z/8"'8")'2/8)>&89>)IEa'
M"S6F6UF6MF6@,9%#%82/(.,S8#%86B6/(6B6.,V6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%#%,"(/' OF-QT'.V' h' NIJM' OA1A2#")[&$)c5/)8"12' )8")>*' aETaQI' a`' C74' OJNN' 7`X*'?\?2FQT'$'h'LIED'O85*'/'h'LIL*'aID'`X*'a`Q*'LIEE'O5555*'/'h'DIa*'eIg*'MIN*'aID'`X*'a`Q*'LINL'O85*'/'h'LIM*'aIE'`X*'a`Q*'LINa'O555*'/'h'aaIa*'DIE*'aIa'`X*' a`Q*'MIMM'O<*'a`Q*'EIFD'O55*'/'h'aIe*'aIa'`X*'F`Q*'aIFa'O<*'aE`Q'HH.I'W")'C74'5&8&'&>)'/$'&%>)).)$8'Z/8"'8")'2/8)>&89>)IEa'
M"S6OTOTLTL6H/&#";/&2.,6F6WF6UO6M&#'*,9%#%;/&2.,S82/(.,V8#%86B6/(6B6.,X6BTITF64'%5"$%#%,"(/' OF,QT'.1' h' NIM' OA1A2#")[&$)c5/)8"12' )8")>*' aETaQI'a`' C74'OJNN'7`X*'?\?2FQT'$'h'LIML'O<*'J`Q*'MILg'O5*'/'h'NIg'`X*'a`Q*'EIJa'O5*'/'h'NIg'`X*'F`Q*'aIFE'O<*'aE`Q'HH.I'W")'C74'5&8&'&>)'/$'&%>)).)$8'Z/8"' 8")'2/8)>&89>)IEF'
M"S6OTOTLTL6H/&#";/&2.,6F6WF6UI6M&#'*,9%#%;/&2.,S82/(.,V8#%86B6/(6B6.,X6BTITF64'%5"$%#%,"(/' OF;QT'.V' h' NIM' OA1A2#")[&$)c5/)8"12' )8")>*' aETaQI' a`' C74'OJNN'7`X*'?\?2FQT'$'h'LILF'O<*'a`Q*'LIeM'O5*'/'h'LID'`X*'a`Q*'LIMF'O5*'/'h'LID'`X*'a`Q*'LIJF'O8*'/'h'LID'`X*'a`Q*'MILg'O5*'/'h'NIg'`X*'a`Q*'EIJa'O5*'/' h'NIg'`X*'F`Q*'aIFE'O<*'aE`Q'HH.I'aF?'C74'OaNN'7`X*'?\?2FQT'$'h'aMeIaD*'aJJILF*'aFNILF'Oj*'/'h'FEIa'`XQ*'aEgIae'O5*'/'h'aIa'`XQ*'aEDILL*'aEJIeE'Oj*'/' h'FIL'`XQ*'aEJIFF'O5*'/'h'ELEIF'`XQ*'aEEIDa'Oj*'/'h'FID'`XQ*'DFIFE*'EMINJ*'ENIaE'HH.I'`470'OR0;*'./A>bWbPQ'%c0T'A&2A5'V#>'?ae`EN_PFC&bE'+7mC&,m' FFMIaJNJ*'V#9$5'FFMIaJNeI'
M"S6OTOTLTL6H/&#";/&2.,6F6WF6UF6M&#'*,9%#%;/&2.,S82/(.,V8#%86B6/(6B6.,X6BTITF64'%5"$%#%,"(/' OF(QI'.V' h' NIM' OA1A2#")[&$)c5/)8"12' )8")>*' aETaQI' a`' C74'OJNN'7`X*'?\?2FQT'$'h'LIea'O5*'/'h'LIg'`X*'a`Q*'LIJe'O8*'/'h'LIe*'NIe'`X*'a`Q*'LIFF'O8*'/'h'LIL'`X*'a`Q*'LIEN'O5*'/'h'LIL'`X*'a`Q*'MIEM'O5*'/'h'NIL'`X*' a`Q*'EIFN'O5*'/'h'NIL'`X*'F`Q*'aIFa'O<*'aE`Q'HH.I'aF?'C74'OaNN'7`X*'?\?2FQT'$'h'aMDIFF*'aJeIaL*'aFaIJD*'aEgIaa*'aELINJ*'aEeIDg'Oj*'/2h'FNIE'`XQ*' aEeINg'Oj*'Kh'MIE'`XQ*'aEJIJN'Oj*'/'h'ELFIL'`XQ*'DFIae*'EMINJ*'EFILJ'Oj*'/'h'aIg'`XQ'HH.I'`470'OR0;*'./A>bWbPQ'%c0T'A&2A5'V#>'?ae`EN_PFC&bE'
+7mC&,m'FFMIaJNJ*'V#9$5'FFMIaFDgI' F%)&$5'I%'"&3)':))$'/<#2&8)5'&<'&'./[89>)T'
M"S6F6UI6MG/(R.,%5.S6F6;/&2.,8#%86B6/(6B6.,V6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%#%,"(/' OF%Q'O%34&(2 56&%+(QT'.V' h' NIF' OA1A2#")[&$)c5/)8"12' )8")>*' aNTaQI'a`'C74'OJNN'7`X*'?\?2FQT'$'h'LIFgGLIEJ'O.*'M`Q*'MIMN'O5*'/'h'NIM'`X*'a`Q*'JIMa'O<*'E`Q*'FIgL'O5*'/'h'NID'`X*'E`Q*'EINN'O<*'F`Q*'aIEg'O<*'aE`Q'HH.I'
aF?'C74'OaNN'7`X*'?\?2FQT'$'h'aMLIea*'aFDIME*'aEDIJE*'aELIeL*'aELIMD*'DEIgE*'LeIaD*'LEIaD*'EJIgD*'aDIEa'HH.I'`470'OR0;*'./A>bWbPQ'%c0T'A&2A5' V#>'?aL`EM_nbF'+7mn,m'FELIaMFa*'V#9$5'FELIaMFDI'
M"S6F6UB6MG/(R.,%5.S$9&6F6/(6F6.,V6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%6#%,"(/)OI%Q'O%5*&(256&%+(QT'.V'h'NIF'OA1A2#")[&$)c5/)8"12')8")>*'aNTaQI'a`'C74' OJNN'7`X*'?\?2FQT'$'h'LIFgGLIEJ'O.*'M`Q*'eIJa'Oj*'/'h'eIL'`X*'a`Q*'JIME'O<*'E`Q*'JIND'O<*'E`Q*'aIgL'O58*'/'h'eIg*'aIF'`X*'F`Q*'aIEg'O<*'aE`Q'HH.I'aF?' C74'OaNN'7`X*'?\?2FQT'$'h'aJFIMJ*'aFgIaE*'aEDIED*'aELILa*'aELIFF*'DFIaF*'LJIFa*'LaIgE*'EJIgD*'aLIFF'HH.I'`470'OR0;*'./A>bWbPQ'%c0T'A&2A5'V#>'
?aL`EM_nbF'+7mn,m'FELIaMFa*'V#9$5'FELIaMFDI'
D&"(4"#4)8#%3/49#/)*%#)&2/)'(&#";%,/39,"#)3"#$%$%#"&'%()%*)",-.(/0)3"&",.R/4)$.)M!!6>!.?S!9!,)OH"$,/)FQC)
f$'#3)$S5>/)5'<A>)Z)5'89:)'Z&<'A"&>%)5'Z/8"'OY6>!.?Q?9?2'ONINND'..#2*'agIJ'.%Q'#>'O>K#Q?9?2'ONINND'..#2*'FIg'.%Q'&$5':/<OH/$&A#2&8#Q5/:#>#$' ONIEN'..#2*'MNIE'.%QI'fV8)>':)/$%'<)&2)5'Z/8"'&'<)H89.*'8")'89:)'Z&<'H9>%)5':1'F'3&A99.S&>%#$'A1A2)<I'W`P'ONIF'.oQ'Z&<'&55)5'&$5'8")'./[89>)' Z&<'<8/>>)5'V#>'M'./$'&8'EN'l?I'f'<#298/#$'#V''_9bn'aIN'7'/$'W`P'ONIE'.oQ'Z&<'&55)5I'fV8)>'<8/>>/$%'V#>'FN'./$*'8")'&2Y1$)'ONIa'..#2Q'Z&<'&55)5I'W")' 89:)'Z&<'<)&2)5'Z/8"'&'<A>)Z'A&H'&$5'8")'./[89>)'Z&<'<8/>>)5'&8'eN'l?'V#>'EJSEL'"I'fV8)>'A##2/$%*'8")'A>95)'>)&A8/#$'./[89>)'Z&<'V/28)>)5'8">#9%"'&'<"#>8' H&5' #V' A)2/8)' :1' >/$</$%' Z/8"' 5/)8"12' )8")>*' &$5' A#$A)$8>&8)5' 9$5)>' 3&A99.I' W")' A>95)' >)</59)' Z&<' H9>/V/)5' :1' </2/A&' %)2' A">#.&8#%>&H"1' OA1A2#")[&$)c5/)8"12')8")>QI'W")'A#$3)></#$'#V'8")'&2Y1$)'&$5'C74'1/)25'#V'8")'H>#59A8'Z)>)'5)8)>./$)5':1'a`'C74'&$&21</<'#V'8")'A>95)'>)&A8/#$' ./[89>)':1'A#.H&>/<#$'Z/8"'8")'/$8)>$&2'>)V)>)$A)'Oa*F*MS8>/.)8"#[1:)$X)$)Q*'&$5'8")'>)%/#<)2)A8/3/81'#V'8")'>)&A8/#$'Z&<'5)8)>./$)5':1'a`'C74'#V'8")' A>95)'>)&A8/#$'./[89>)I'
F6M!.3,%8/(&.,'4/(/;/&2.,S6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%#%,"(/'OL"QT'.V'h'NIJ'OA1A2#")[&$)c5/)8"12')8")>*'aNTaQI'a`'C74'OJNN'7`X*'?e\eQ'$'h' MIeD'OH*'/'h'EIa'`X*'a`Q*'EILe'O8*'/'h'LIF'`X*'E`Q*'EIEe'O8*'/'h'LIF'`X*'E`Q*'aIeNGaIMa'O.*'E`Q*'aIJLGaIFg'O.*'E`Q*'aIaE'O<*'aE`Q'HH.I'W")'C74'5&8&'&>)' /$'&%>)).)$8'Z/8"'8")'2/8)>&89>)IEJ'
F6M!.3,%2/56B6/(6B6.,S6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%#%,"(/' ON"QT'.V' h' NIJ' OA1A2#")[&$)c5/)8"12' )8")>*' aNTaQI' a`' C74' OJNN' 7`X*' ?\?2FQT'$' h' eIMgGeIMF'O.*'a`Q*'EIaFGEINJ'O.*'J`Q*'aIeNGaIMe'O.*'J`Q*'aIEM'O<*'aE`QI'W")'C74'5&8&'&>)'/$'&%>)).)$8'Z/8"'8")'2/8)>&89>)IEM'
M"S6F6UM?'2.4#%*9#"(6IMF:S6.,'4/(/S;/&2.,V6OTOTLTL6&/&#";/&2.,6BTITF64'%5"$%#%,"(/'OL$QT'.V'h'NIJ'OA1A2#")[&$)c5/)8"12')8")>*'aNTaQI'a`'C74'OJNN' 7`X*'?\?2FQT'$'h'MIFaGMIEe'O.*'a`Q*'JIEg'O5*'/'h'aIM'`X*'E`Q*'FIgF'O8*'/'h'LIN'`X*'E`Q*'EIDFGEILe'O.*'E`Q*'aIEL'O<*'aE`Q'HH.I'aF?'C74'OaNN'7`X*'
?\?2FQT'$'h'aeMINJ*'DFIaN*'LFIEJ*'egIFN*'FFIFg*'EMINF'HH.I'`470'OR0;*'./A>bWbPQ'%c0T'A&2A5'V#>'?ae`EN_PFC&bE'+7mC&,m'EFFIaFEa*'V#9$5'EFFIaFNMI'
+3-(%1,/4A;/(&0))
!('8"&$Y<'8")'?"/$&'0A"#2&><"/H'?#9$A/2'V#>'="\'%>&$8I'
Z/.1%#40<'?&8&21</<'q'A#HH)>'q'A1A2#5)[8>/$<'q'>)%/#<)2)A8/3/81'q'<9H>&.#2)A92&>'A")./<8>1'
+a,' &Q'7I'r9/8)8*'=I'!"&$%*'PI'7&>A)2#*'?I'W9%$1*'KI'K/.@$)XS_&>:)>#*'bI'_9>/)X*'?I'f.&8#>)*'sI'7#9>/t<S7&$<91*'KI'r#55&>5*'oI'P)$<8)>:&$Y*'-I'!"&$%*'0I' 4#2&$5*' 7I' 7@$&$5*' 7I' 0#22#%#9:*'7*8+9:2 ;)+%:2 <*':2 "-:2F[BI*2 =>*' LEaFSLEaDd' :Q' =I' !"&$%*' ?I' W9%$1*' KI' 7)/]/5)' 09u>)X*' 7I' r9/8)8*' RI' \)>&8*' CI' s&$8"91$)*'-I'!"&$%*'bI'_/<8>/*'sI'7#9>/t<S7&$<91*'7I'7@$&$5*'0I'4#2&$5*'oI'P)$<8)>:&$Y*'7I'0#22#%#9:*';)+%'F[B\*'?*'aLJSagaI'
+E,' @&(2(+A5+96B26++C'&Q'0I'`I'fI'7I'o))$5)><*'4I'r>&.&%)S\#>/&*'_I'5)'_>9/$*'KI'CI'`I'4))Y*';)+%:2D&E:2.+A:'F[BL*'FF*'JFFSJJDd':Q'WI';Z&<&Z&I'G+'(3)+-(&*2 H+'':'F[B\*'=I*'JEaLSJEEed'AQ'0I'4#2&$5*'KI'7)/]/5)'09u>)X*'7I'0#22#%#9:*';)+%:2"J(:2/:'F[B]*'>F*'ESaEd'5Q';I'0/$"&'=&>8"&*'0I'79Y")>]))*'<*&(8:2;)+%:' F[B]*'=K*'JENMSJEEad')Q'KI'-&$%*'_I'?"&8)2)8*'\I'`@>&928*'KIS=I'\98&<8&*'fI'7&>8/$)X*'"J(:2/:2L(8:2;)+%I'F[B]*'FM*'MeaDSMeEDd'VQ'7I'b88)*'7;D2;3'3N:2F[BN*' O*'eJgaSeMaNd'%Q'7I'4&1$&2*'=I'_&22)<8)>*'fI's/5&2SP)>>&$*'=I'(I'CI'7I's&$'o))9Z)$*';)+%:2D&E:2.+A:'F[BO*'F?*'aLFJSaLDLd'"Q'?I'KI'_>#Z$*'PI'\I'W#<8)*'4I'
rI'_)>%.&$*'nI'CI'4&1.#$5*';)+%:2.+A:'F[BL*'MM=*'FNaESFNFMd'/Q'oI'KI'K#$%Y/$5*'vI'?&9.)<*'fI'=I'WI'`&>8)$5#>H*'KI'CI'`I'4))Y*)7EE:2;)+%:2.+6:'F[B]*'
=M*'EaaMSEaEDd']Q'?I'W&$*'\&$5&$'?"9*'vI'W&$%*'-I'o/9*'(I'v9&$*'-I'?9/*';)+%:2"J(:2/:'F[B^*'EM*'eeESeLEd'YQ'?I'\)>&)58*'\I'f<8>9A*';&&(-:2;)+%:2.+A:' F[BN*'?>F*'aNeSaEEI'
+F,' @&(2(+A5+96B26++C'&Q'`I'-#<"/5&*'7;D2;3'3N:2F[BN*'O*'aLggSaDaad':Q'KI'-9$*'7653*2/:2L(8:2;)+%:'F[BI*'>*'aNaeSaNEMd'AQ'\I'`)../$%*'4I'P>/8X).)/)>*'0I'fI' ()<8A#88*'(I'oI'0&$8#<*'=I'rI'08))2*';)+%:2D&E:2.+A:'F[B]*'FK*'LJLLSLJgJI'
+J,' =I'!"&$%*'KI'7)/]/5)'09u>)X*'WI'\>/&$8*'RI'\)>&8*'-I'!"&$%*'7I'7@$&$5*'0I'4#2&$5*'7I'0#22#%#9:*'7*8+9:2;)+%2<*':2"-:'F[B\*'=O*'aNDEaSaNDEMI'
+M,' &Q'`I'K&$%*'fI'4I'!"9%>&2/$*'-I'o))*'fI'`I'`#3)15&*'/:27%:2;)+%:2D&E:2F[BB*'M??*'LDMgSLDLad':Q'KI'`I'7##$*'`IS-I'K9$%*'-I'KI'o))*'0I'(I'o))*'KI'-9$*'KI'-I' o))*'L(83*&%+'3NN5E6*'F[BL*'?F*'EaMaSEaMgd'AQ'\I'0I'o&/8&>*'RI'-I'W<9/*'KI'=I'0&5/%"/*'L(83*&%+'3NN5E6*'F[[N*'>=*'EJNMSEJNDI'
+e,' W")'A#HH)>SA&8&21X)5'A&>:#:#>&8/#$'#V'&2Y1$)<'Z&<'/$/8/&221'>)H#>8)5'/$'ENaE*'<))T'&Q'oI'!"&$%*'KI'?")$%*'?I'_I'?&>>1*'!I'`#9*'/:27%:2;)+%:2D&E:'F[BF*' M?F*'aJFaJSaJFaLd':Q'4I'f2V&>#*'fI'=&>>&*'KI'f2).u$*'KI'oI'rI'49&$#*'7I'W#>8#<&*'/:27%:2;)+%:2D&E:'F[BF*'M?F*'aMaeMSaMaeDI'
+L,' @&(2&')+(2+,3%$N+62&12E3(P&P&(3'5&*B26++T'&Q'`I'-#<"/5&*';I'n&%)19Y/*'nI'W&Y&Y/*'L(8:2H+'':'F[BI*'M=*'gMESgMMd':Q'?IS?I'W&/*'7IS0I'-9*'-ISoI'?")$*'(IS`I'
?"9&$%*'WIS`I'o/$*'rI'=I'fI'-&H*'WISrI'b$%*';)+%:2;&%%J*:'F[BO*'=Q*'JFJJSJFJeI' +D,' @&(232(+A5+9B26++C'-I'0"/./X9*'7I'n&$&/*'G+'(3)+-(&*2H+'':'F[BO*'==*'FLELSFLFLI'
+g,' P#>'>)V)>)$A)<'Z/8"'/$8)>$&2'&2Y1$)<*'6++T'&Q'?IS?I'W&/d'7IS0I'-9d'-ISoI'?")$d'(IS`I'?"9&$%d'WIS`I'o/$d'rI'=I'fI'-&Hd'WISrI'b$%*';)+%:2;&%%J*:'F[BO*'=Q*' JFJJSJFJed':Q'-I'\I'_/5&2d'PI'o&X>)%d'?I'0I'KI'?&X/$*'7;D2;3'3N:'F[BO*'F*'aMeJSaMegd'AQ'WI';8#"*'-I'0"/./X9*'7I'n&$&/*'/:27%:2;)+%:2D&E:'F[BN*'M?I*'LMEDS LMFaI'
+aN,' P#>'8)>./$&2'&2Y1$)<*'6++T'_I'79$*'0I'n/.*'`I'-##$*'nI'`I'n/.*'-I'o))*'/:2L(8:2;)+%:'F[B\*'I>*'eFJgSeFMLI'
+aa,' (/8"'!S&5&.&$812S<9:<8/898)5'C`?S?9'A#.H2)[)<*'/8'Z&<'<9%%)<8)5'8"&8'A#HH)>G&2Y1$)'A##>5/$&8/#$'/<'8")'H>#59A8S5)8)>./$/$%'<8)H*'>&8")>'8"&$'&2Y1$)' /$<)>8/#$'/$8#'?9G_':#$5I'W"/<'A#925'&AA#9$8'V#>'8")'2#Z'<)$</8/3/81'#V'>)%/#<)2)A8/3/81'8#'<9:<8>&8)')2)A8>#$/A')VV)A8*'6++'>)VI'M&I'
+aE,' =>)3/#9<'A&2A92&8/#$<'#$'8")'A#HH)>SA&8&21X)5'&2Y)$)'A&>:#:#>&8/#$'>)&A8/#$':1'-9'&$5'P9p<'%>#9H'<9%%)<8)5'8"&8'8")'>)&A8/#$'Z/8"'&2Y12'"&2/5)<'/<'8")'
>&8)S5)8)>./$/$%'<8)H'6++T'!IS-I'v9*'-IS-I'K/&$%*'(I'09*'`IS!I'-9*'-I'P9*';)+%:2"J(:2/:'F[BN*'>>*'aJeaaSaJeaLI'
+aF,' @&(25*5'53N2+,3%$N+62&123NR+*+2ESEN503'5&*B26++T'&Q'?ISWI'-&$%*'!ISwI'!"&$%*'`I'W&]955/$*'?IS?I'(9*'KI'o/&$%*'KIS`I'o/9*'-I'P9*'7I'?X1X)Z<Y&*'=I'rI'08))2*'WI' _I'7&>5)>*'oI'o/9*27*8+9:2;)+%:2<*':2"-:2F[BF*'=M*'MEDSMFEd':Q'nI'n9:#8&*'RI'-&.&.#8#*'`I';8#*2/:27%:2;)+%:2D&E:'F[BI*'M?=*'EeFMSEeJNI'
+aJ,' &Q'<*'(3%&N+EJN3(23--5'5&*2&*2E&*4J83'+-2R+'&*+6C'=I'o/9*'-I'P9Y9/*'=I'W/&$*'!I'WI'`)*'?I'-I'09$*'CI'-I'(9*'rI'wI'o/$*'/:27%:2;)+%:2D&E:'F[BI*'M?=*'aaLNNS aaLNFd' :Q'<*'(3%&N+EJN3(2 ESEN503'5&*2 &*2 65N5E&*T'+')+(+-2 3NRSNP(&%5-+6C' nI' n9:#8&*' `I' ;Z&.#8#*' RI' -&.&.#8#*' `I' ;8#*'L(8:2 H+'':'F[BL*'MK*' eENSeEFd' AQ'
<*'(3%&N+EJN3(2ESEN503'5&*2&12$(&$3(8SN2+')+(623*-23%5*+62N5*R+-2'&23NRSN)3N5-+6C'`I';Z&.#8#*'-I'bX&Z&*'nI'n9:#8&*'`I';8#*'/:2L(8:2;)+%:'F[B\*'I>*'aNMeFS aNMLFd'5Q'@&(%3N23NNSNP&(3'5&*2&123NRS*+6B2D!>UT'S$+25*'(3%&N+EJN3(2ESEN503'5&*C'PI'!"&$%*'0I'(&$%*'!I'o/9*'-I'_&/*'rI'!"9*'G+'(3)+-(&*2H+'':'F[B\*'=I*'aJJDS aJMEd')Q'<*'(3%&N+EJN3(2ESEN503'5&*2&123(SNT6JP'5'J'+-25*'+(*3N23NRS*+6C'0I'!"#9*'PI'-9&$*'7I'r9#*'rI'(&$%*'vI'W&$%*'(I'!"&#*'L(8:2H+'':'F[B]*'>Q*'eLaNS eLaJd'VQ'<*'(3%&N+EJN3(23--5'5&*2&*2+$&,5-+623*-2E&*4J83'+-2+6'+(6C20IS`I'n/.So))*';I'f2#$<#*'=I'7&92)x$*'4I'rx.)X'f>>&1u<*'KI'?I'?&>>)8)>#*'7;D2;3'3N:' F[B]*'I*'DggFSgNNMI'
+aM,' W")')VV)A8'#V'C&b'_9'#$'8")'.)A"&$/<.'#V'8")'A#HH)>SA&8&21X)5'A&>:#:#>&8/#$'>)&A8/#$'Z&<'<895/)5'/$'5)8&/2<':1'7&92)x$*'f>>&1u<'&$5'?&>>)8)>#*'6++'>)VI' aJVI';$'A#$8>&<8'8#'>)VI'aJ)*'&'$#$>&5/A&2'H>#A)<<'Z&<'H>#H#<)5'V#>'^)[#^'A1A2/X&8/#$'Z/8"'&$'/$8)>$&2')H#[/5)'&<')2)A8>#H"/2)'&$5'?9?2c=?1F'&<'A&8&21<8I' +ae,' ;8'/<'A#$A)/3&:2)'8"&8'&'A#.H)8/8/3)'>&5/A&2'^)$5#^'A1A2/X&8/#$'2)&5<'8#'N"'V#>.&8/#$I'\)A>)&</$%'8")''_9bn'A#$A)$8>&8/#$'A#925'5)A>)&<)'8")'A#$A)$8>&8/#$'
#V'O=QS?9;G_H/$'<H)A/)<'Z"/A"'A#925':)'/$3#23)'/$'8")'V#>.&8/#$'#V'&'H>/.&>1'&2Y12'>&5/A&2*'6++'>)VI'aJ)I'
+aL,' V)&'&E3'3NS'5E2"W#256&%+(503'5&*62)3A+2P++*2(+E+*'NS2-+6E(5P+-B26++T'&Q'KI'KI'7#22#1*'KI'_I'7)88)>$/A"*'?I'rI'\&$/2/9A*'fI'KI'_I'(&8<#$*'4I'r/2.#9>*'7*8+9:2
;)+%:'F[B]*'M?Q*'FEEESFEEed':Q'(I'?&/*'`I'P&$*'\I'\/$%*'-I'!"&$%*'(I'(&$%*';)+%:2;&%%J*:'F[B\*'=?*'aEgaDSaEgEaI' +aD,' WI';<"/Y&Z&*'WI'7/X98&*'nI'`&%/Z&>&*'WI'f/Y&Z&*'WI'n95#*'0I'0&/8#*'/:2L(8:2;)+%I'F[[I*'OI*'FLNESFLNMI'
+ag,' WI'`&>&5&*'nI'79>&.&8<9*'nI'7/X9$&<"/*'?I'n/8&$#*'\I';.&#Y&*''WI'P9]/Z&>&*'`I'n&8&#Y&*'/:2L(8:2;)+%:'F[[]*'K?*'EJgSEMDI' +EN,' KI'_>)/8)$V)25*'KI'49/X*'7I'\I'(#5>/A"*'vI'`9*'/:27%:2;)+%:2D&EI'F[BI*'M?=*'aENNJSaENaEI'
+Ea,' KI'KI'7#22#1*''KI'_I'7)88)>$/A"*'?I'rI'\&$/2/9A*''fI'KI'_I'(&8<#$*'4*'r/2.#9>*'7*8+9:2;)+%:2<*':2"-:2F[B]*'M?Q*'FEEESFEEeI' +EE,' 4I'f2V&>#*'fI'=&>>&*'KI'f2).&$*'KI'oI'rI'49&$#*'7I'W#>8#<&*'/:27%:2;)+%:2D&E:'F[BF*'M?F*'aMaeMSaMaeDI'
+EF,' ?I'(&$%*'?I'(9*'0I'r)*'7;D2;3'3N:'F[BN*'O*'LMDMSLMDgI'
+EJ,' ;I'fI';I'7Y"&2/5*'4I'_I'?#&H)<*'0I'CI'R5)<*'\I'CI'?#3)$8>1*'PI'RI'0I'0#9X&*'4I'oI'W"#.&<*'KI'KI'`&22*'0I'_/*'!I'o/$*'WI'_I'7&>5)>*'X3N'&*2G(3*6I'F[[]*'I*'aNMMS aNeJI'
+EM,' CI'0)2&$5)>*'_I'(/221*'nI'KI'0X&:x*'7*8+9:2;)+%:2<*':2"-:'F[B[*'FY*'JNMaSJNMFI'
