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a. Strained sulfonamides (Doyle and Sigman) MeO Ts NiCl2·glyme (,!.+0$!0$%)*(1$!%,/!)+..+,'>!3*('(=$/!$'$)*0+&#('$2F!23)#! N I OMe chiral bioxazoline %2! %'?>'! #%'(/$29! C30*#$0.+0$F! *#$! %.(/+! '$%1(,4! 40+3&2! + NaI, Mn0, TMSCl NHTs 4$,$0%*$/!)%,!2$01$!%2!2*0+,4!'(4%,/2F!0$23'*(,4!(,!)%*%'>2*! 3 73% yield, 94% ee /$%)*(1%*(+,9 !!"#$! /(2)+1$0>! +-! ,$;! )%*%'>2*2! )%&%8'$! +-! b. Ammonium salts (Martin) $,4%4(,4! 567! 8+,/2! ;+3'/! (.&0+1$! +30! %8('(*>! *+! /$2(4,! Me I CO H 0$%)*(+,2!*#%*!$A&'+(*!0$*()$,*!$'$)*0+&#('$2F!%2!;$''!%2!(,< NiCl2 2 NMe phenanthroline ligand 3 Me -+0.!-3*30$!)%*%'>2*!/$2(4,9!! + CO2 Ph Mn0 50+22<$'$)*0+&#('$! )+3&'(,4! MDE5N! 0$%)*(+,24! +-! %.(,$! Ph 81% yield /$0(1%*(1$2! %0$! 0%0$F! %,/! )300$,*! $A%.&'$2! 0$L3(0$! 238< c. Katritzky salts (Watson) NiCl ·dme 5!6!7!8 Me Me N 2 2*0%*$2!;#$0$!*#$!567!8+,/!#%2!8$$,!%)*(1%*$/F !$(*#$0! bipyridine ligand N + 8>!(,)+0&+0%*(+,!(,*+!%!2*0%(,$/!0(,4!+0!8>!-+0.%*(+,!+-!%,! N 0 Ph Br MgCl2, Mn %..+,(3.!2%'*99!10!11!12!C+0!$A%.&'$F!*#$!B+>'$!%,/!O(4.%,! BF4 Ph Me 85% yield '%8+0%*+0($2! 0$&+0*$/! *#$! ,()?$'<)%*%'>=$/! )0+22< d. Sulfonamides (This work) $'$)*0+&#('$!)+3&'(,4!0$%)*(+,!+-!2*0%(,$/F!8$,=>'()!23'-+,>'! Ts Me Ni Ts Ni %=(0(/(,$2!;(*#!%0>'!(+/(/$2!*+!4$,$0%*$!$,%,*(+$,0()#$/!P< N catalyst Ar N catalyst Ar NHTs " MeMgI MeMgI %0>'&#$,$*#>'23'-+,%.(/$2! MO)#$.$! Q%N9 ! @%0*(,! %,/! )+< Ar Cl Ar Cl ;+0?$02!/$1$'+&$/!*#$!,()?$'<)%*%'>=$/!)0+22<$'$)*0+&#('$! > 20:1 dr > 20:1 dr )+3&'(,4!0$%)*(+,!+-!8$,=>'()!%..+,(3.!2%'*2!;(*#!)%08+,! /(+A(/$!*+!%--+0/!8$,=>'()!)%08+A>'()!%)(/2!MO)#$.$!Q8N9#$! G,! *#(2! .%,32)0(&*F! ;$! /$2)0(8$! *#$! -(02*! )0+22< H$)$,*'>F! *#$! R%*2+,! '%8+0%*+0>! 0$&+0*$/! *#$! ,()?$'< $'$)*0+&#('$! )+3&'(,4! 0$%)*(+,! +-! 8$,=>'()! 23'-+,%.(/$2! )%*%'>=$/!)0+22<$'$)*0+&#('$!)+3&'(,4!0$%)*(+,!+-!S%*0(*=?>! MO)#$.$! Q/N913! K'?>'! )#'+0(/$2! %,/! 8$,=>'()! 23'-+,%.(/$2! 2%'*2! ;(*#! %0>'! 80+.(/$2! MO)#$.$! Q)N9#%! "#$2$! (.&+0*%,*! %0$! $,4%4$/! (,! %,! (,*0%.+'$)3'%0! ,()?$'<)%*%'>=$/! DE5! /$1$'+&.$,*2!#%1$!/$.+,2*0%*$/!*#$!-$%2(8('(*>!+-!%&&'>< 0$%)*(+,! *+! %--+0/! .+,+2382*(*3*$/! )>)'+&0+&%,$29! K//(< (,4!%.(,$!/$0(1%*(1$2!%2!$'$)*0+&#('$2!(,!)0+22<$'$)*0+&#('$! *(+,%''>F! !<*+2>'<T<)#'+0+&(&$0(/(,$2! 3,/$04+! %! 2*$0$+2$< '$)*(1$! 0(,4! )+,*0%)*(+,! *+! %--+0/! *0%,2<2382*(*3*$/! )>)'+< Ni Source (5 mol %) Me Ts Ligand (5 mol %) &0+&%,$2!;(*#!#(4#!/(%2*$0$+2$'$)*(1(*>9!"#$2$!0$23'*2!%0$! N Additive (1 equiv) F C O F3C ,+*$;+0*#>! 8$)%32$! *#$! %8('(*>! *+! .%,(&3'%*$! *#$! 2*03)< 3 Cl MeMgI (2 equiv) O *30$2!+-!23'-+,%.(/$2!(2!1%'3%8'$!/3$!*+!*#$(0!&0$1%'$,)$!(,! 1 PhMe, rt, 24 h 2 *#$! &#%0.%)$3*()%'! (,/32*0>914! C+0! $A%.&'$F! 23'-+,%.(/$< Entry Ni Source Ligand Additive Yield (%)a )+,*%(,(,4!)+.&+3,/2!%0$!?,+;,!*+!&+22$22!%!;(/$!1%0($< *>! +-! 8(+'+4()%'! &0+&$0*($2F! (,)'3/(,4! %,*(<(,-'%..%*+0>F! 1 ((R)-BINAP)NiCl2 none MgI2 77 %,*(<#>&$0*$,2(1$! %,/! %,*(<)+,13'2%,*! %)*(1(*>9! H$)$,*! 2 ((R)-BINAP)NiCl2 none none 63 b 2*3/($2!#%1$!/$.+,2*0%*$/!*#%*!23'-+,%.(/$2!)%,!.$/(%*$! 3 ((R)-BINAP)NiCl2 none MgI2 40 c &0+*$(,<&0+*$(,! (,*$0%)*(+,2! (,1+'1$/! (,! )%,)$0! &0+40$2< 4 ((R)-BINAP)NiCl2 none MgI2 77 2(+,! %,/! (,#(8(*! ,$30+*0%,2.(**$0! 8(+2>,*#$2(2915! G,! *#(2! 5 Ni(cod)2 rac-BINAP MgI2 27 .%,32)0(&*F! ;$! 0$&+0*! *#$! 2*03)*30%'! 0$%00%,4$.$,*! +-! 6d Ni(cod) rac-BINAP MgI 23 23'-+,%.(/$2U*#$!*0%,2-+0.%*(+,!+-!!<*+2>'&(&$0(/(,$2!*+! 2 2 !<*+2>'M%.(,+$*#>'N)>)'+&0+&%,$2U%2! ;$''! %2! 2$**(,4! *#$! 7 NiCl2(dme) rac-BINAP MgI2 29 -+3,/%*(+,! -+0! -30*#$0! /$1$'+&.$,*! +-! ,()?$'<)%*%'>=$/! 8 NiCl2(dme) rac-BINAP none 8 DE5!0$%)*(+,2!+-!3,2*0%(,$/!%,/!,$3*0%'!%.(,$!/$0(1%*(1$29! 9 NiCl2(dme) XantPhos none 0 HEOJV"O!K7B!BGO5JOOGI7! 10 NiCl2(dme) DPEPhos none 16 11 NiCl (dme) BPhen none 11 =*>*406+*95, 0<, #84<09;+7?*, &/011234*(5/06)74*, 2 &086479:,%*;(5709.!R$!8$4%,!8>!$1%'3%*(,4!*#$!(,*0%.+< 12 NiCl2(dme) SiMes·HBF4 none 15 '$)3'%0!)0+22<$'$)*0+&#('$!)+3&'(,4!0$%)*(+,!+-!23'-+,%.(/$! 13 NiCl2(dme) PCy3 none 28 -9! "#$! +&*(.%'! DE5! 0$%)*(+,! )+,/(*(+,2! $.&'+>$/! %(0< 14 NiCl2(PCy3)2 none none 7 15 none none none 0 2*%8'$! MM"N<WG7KXN7(5'%! %2! *#$! )%*%'>2*F! @$@4G! %2! *#$! 0$< 16e ((R)-BINAP)NiCl none Mg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e Ts ((R)-BINAP)NiCl (5 mol%) R N 2 Ar N ((R)-BINAP)NiCl2 (5 mol%) MeMgI (2 equiv) Ar Cl X NHR PhMe, rt, 24 h MgI2 (1 equiv) MeMgI (2 equiv) 8a–d PhMe, rt, 24 h 9a–d > 20:1 dr > 20:1 dr S Entry R X SM Yield 9 (%)a Recovered 8 (%)a Me O N O 1 Ts Cl 8a 96 < 2 3 4 5 2 Ns Cl 8b < 5 < 5 82%b 59%a (73%)b 53%a,c (80%)b,c Me 3 Tf Cl 8c > 99 < 2 b F N 4 Ts Cl 8d 32 34 5 Ts F 8e < 2 < 2 S N 6 Ts Br 8f < 12 < 2 6 7 a,d 64% 65%b,c &"#$%&! &$'$()#*$&! +,! #-! ./0! +12$&! 3*! 43)51(#23*! '3! &D23%1'$&! "#$%&:! '"#$%&! &$'$()#*$&! +,! #-! ./0! +12$&! 3*! 678/9! 12! #*'$(*1%! 2'1*&1(&:! '82,! I! JH 43)51(#23*!'3!678/9!12!#*'$(*1%!2'1*&1(&:!)@!$EF#G!/CD%!1&&H K'(#?%F3(3)$'7,%L+$*M$*$2F%?3*,%:! * $&:! @:;!$EF#G!/CD%!1&&$&:! R(*#!!<*+2>'!%,/!!<*0(-'>'&(&$0(/(,$2!23))$22-3''>!$,4%4< =*>*406+*95, 0<, L76*/7?79*, %79:, &095/;(5709., R$! (,4!(,!*#$!(,*0%.+'$)3'%0!)0+22<$'$)*0+&#('$!)+3&'(,4!0$%)<