Double Functionalization of Styrenes by Cu-Mediated Assisted Tandem Catalysis

Article abstract of DOI:10.1002/ejoc.201900088

The double functionalization of styrenes through Cu-mediated assisted tandem catalysis was developed. The reaction was initiated by Cu-catalyzed aziridination and the subsequent nucleophilic ring-opening, which was triggered by the addition of (NH₄)₂S₂O₈ as an oxidant of Cu-catalyst to form a variety of C–C and C–X bonds. The expansion to three contiguous catalytic cycles led to the synthesis of functionalized indolines by one-pot operation.

Full text of DOI:10.1002/ejoc.201900088

A Journal of
Accepted Article
Title: Double Functionalization of Styrenes by Cu-mediated Assisted
Tandem Catalysis
Authors: Daichi Kawauchi, Hirofumi Ueda, and Hidetoshi Tokuyama
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201900088
Link to VoR: http://dx.doi.org/10.1002/ejoc.201900088
Supported by

10.1002/ejoc.201900088
European Journal of Organic Chemistry
COMMUNICATION
ꢀꢁꢂ ꢃꢄꢅꢆꢂꢇꢈꢉꢊꢁꢇꢋꢃꢊꢌꢋꢉꢊꢁꢇꢅꢁꢍꢅꢎꢉꢏꢐꢄꢇꢄꢑꢅ ꢏꢅꢒꢂꢓꢔꢄꢕꢊꢋꢉꢄꢕꢅꢖꢑꢑꢊꢑꢉꢄꢕꢅꢗꢋꢇꢕꢄꢔꢅ
ꢒꢋꢉꢋꢃꢏꢑꢊꢑꢅ
ꢀꢁꢂꢃꢄꢂꢅꢆꢁ-ꢁ+ꢃꢄꢂ:ꢁ;2ꢅ ꢂ(%ꢇ+#ꢂꢅꢈꢉꢊꢁ:ꢁ;2ꢅꢁ$ꢊꢅ ꢂꢊꢉ*%)ꢄꢂꢅꢋ%!+/ꢁ#ꢁ<:ꢁ;ꢅ
ꢖ ꢑꢉꢐꢋꢈꢉꢘꢅ ꢋꢄꢉꢅ ꢊ%+ꢌ"ꢉꢅ ꢇ+$ꢃ*ꢂ%$ꢁ"ꢂ0ꢁ*ꢂ%$ꢅ %ꢇꢅ )*/(ꢉ$ꢉ)ꢅ *ꢄ(%+ꢍꢄꢅ ꢎ+6
2'$ꢀꢅ3ꢀ" 2 *712ꢀ!7ꢀ2'$ꢀ ##(2(-,ꢀ-%ꢀ ,ꢀ-6(# ,2ꢀ 1ꢀ ꢀ20(&&$0ꢍꢀ ,#ꢀ2'$ꢀ
#ꢉꢊꢂꢁ*ꢉꢊꢅꢁ))ꢂ)*ꢉꢊꢅ*ꢁ$ꢊꢉ#ꢅꢃꢁ*ꢁ"/)ꢂ)ꢅ-ꢁ)ꢅꢊꢉ,ꢉ"%&ꢉꢊ3ꢅꢋꢄꢉꢅ(ꢉꢁꢃ*ꢂ%$ꢅ 13!1$/3$,2ꢀ ##(2(-,ꢀ-%ꢀ ꢀ,3"*$-.'(*$ꢀ2-ꢀ.0-+-2$ꢀ0(,&ꢆ-.$,(,&ꢂꢏꢄꢀ
-ꢁ)ꢅ ꢂ$ꢂ*ꢂꢁ*ꢉꢊꢅ ꢌ/ꢅ ꢎ+6ꢃꢁ*ꢁ"/0ꢉꢊꢅ ꢁ0ꢂ(ꢂꢊꢂ$ꢁ*ꢂ%$ꢅ ꢁ$ꢊꢅ *ꢄꢉꢅ )+ꢌ)ꢉ'+ꢉ$*ꢅ 5(2'ꢀ 2'$ꢀ "2(4 2(-,ꢀ -%ꢀ 8(0(#(,$ꢀ 0(,&ꢀ !7ꢀ ꢅ3ꢀ ꢊꢋꢋꢀ -0ꢀ ꢋꢋꢋꢌꢐꢆ" 2 *712ꢀ
$+ꢃ"ꢉ%&ꢄꢂ"ꢂꢃꢅ(ꢂ$ꢍ6%&ꢉ$ꢂ$ꢍ2ꢅ-ꢄꢂꢃꢄꢅ-ꢁ)ꢅ*(ꢂꢍꢍꢉ(ꢉꢊꢅꢌ/ꢅ*ꢄꢉꢅꢁꢊꢊꢂ*ꢂ%$ꢅ%ꢇꢅ 1'-3*#ꢀ%30,(1'ꢀ2'$ꢀ#$1(0$#ꢀ#-3!*$ꢀ%3,"2(-, *(8$#ꢀ.0-#3"2ꢉꢅ
8ꢏ C9AꢐAꢑFꢅꢁ)ꢅꢁ$ꢅ%.ꢂꢊꢁ$*ꢅ%ꢇꢅꢎ+6ꢃꢁ*ꢁ"/)*ꢅ*%ꢅꢇ%(#ꢅꢁꢅ,ꢁ(ꢂꢉ*/ꢅ%ꢇꢅꢎ7ꢎꢅ
ꢁ$ꢊꢅꢎ7ꢒꢅꢌ%$ꢊ)3ꢅꢋꢄꢉꢅꢉ.&ꢁ$)ꢂ%$ꢅ*%ꢅ*ꢄ(ꢉꢉꢅꢃ%$*ꢂꢍ+%+)ꢅꢃꢁ*ꢁ"/*ꢂꢃꢅꢃ/ꢃ"ꢉ)ꢅ
"ꢉꢊꢅ *%ꢅ *ꢄꢉꢅ )/$*ꢄꢉ)ꢂ)ꢅ %ꢇꢅ ꢇ+$ꢃ*ꢂ%$ꢁ"ꢂ0ꢉꢊꢅ ꢂ$ꢊ%"ꢂ$ꢉ)ꢅ ꢌ/ꢅ %$ꢉ6&%*ꢅ
ꢅ
ꢊ ꢋꢌꢍꢉꢎꢏꢀꢑ&*ꢂ#ꢂ0ꢁ*ꢂ%$ꢅ%ꢇꢅ(ꢉꢁꢃ*ꢂ%$ꢅꢃ%$ꢊꢂ*ꢂ%$)ꢅꢅ
Catalyst (5 mol%)
PhI=NTs (1.0 eq)
Oxidant (2.0 eq)
MeOH (50 eq)
%&ꢉ(ꢁ*ꢂ%$ꢙꢅꢅ
MS4Å[a]
OMe
NTs
Ph
NHTs
Ph
Ph
MeCN (0.5 M)
50 °C, Time
3a
1a
ꢑ,207ꢀ
2a
ꢒ6(# ,2ꢀ
rt, 24 h;
ꢀ
ꢓ($*#ꢀꢂꢔꢄꢂ!ꢄ
ꢀ
ꢀꢁꢂꢃꢄꢅꢆꢇꢂꢈꢄꢁꢉ
ꢅ 2 *712ꢀ
ꢁ(+$ꢀꢂ'ꢄꢀ
ꢋꢁ$ꢊꢉ#ꢅ ꢃꢁ*ꢁ"/)ꢂ):@;ꢅ ꢂ$,%",ꢉ)ꢅ ꢂ$*ꢉꢍ(ꢁ*ꢉꢊꢅ ꢃꢁ*ꢁ"/*ꢂꢃꢅ )/)*ꢉ#)ꢅ ꢂ$ꢅ
-ꢄꢂꢃꢄꢅ )ꢉ'+ꢉ$*ꢂꢁ"ꢅ *(ꢁ$)ꢇ%(#ꢁ*ꢂ%$)ꢅ &(%ꢃꢉꢉꢊꢅ ,ꢂꢁꢅ *-%ꢅ %(ꢅ #%(ꢉꢅ
#ꢉꢃꢄꢁ$ꢂ)*ꢂꢃꢁ""/ꢅ ꢊꢂ)*ꢂ$ꢃ*ꢅ ꢃꢁ*ꢁ"/*ꢂꢃꢅ &(%ꢃꢉ))ꢉ)ꢅ ꢂ$ꢅ %$ꢉꢅ &%*3ꢅ ꢓ#%$ꢍꢅ
*ꢄ(ꢉꢉꢅ*/&ꢉ)ꢅ%ꢇꢅ*ꢁ$ꢊꢉ#ꢅꢃꢁ*ꢁ"/)ꢂ)2ꢅ$ꢁ#ꢉ"/ꢅ%(*ꢄ%ꢍ%$ꢁ"62:Aꢁ6ꢉ;ꢅꢁ+*%62:Aꢇ6
ꢄ;ꢅꢁ$ꢊꢅꢁ))ꢂ)*ꢉꢊ6*ꢁ$ꢊꢉ#ꢅꢃꢁ*ꢁ"/)ꢂ)2:Aꢂ6$;ꢅꢁ))ꢂ)*ꢉꢊꢅ*ꢁ$ꢊꢉ#ꢅꢃꢁ*ꢁ"/)ꢂ)ꢅꢄꢁ)ꢅ
ꢁ**(ꢁꢃ*ꢉꢊꢅꢃ%$)ꢂꢊꢉ(ꢁꢌ"ꢉꢅꢁ**ꢉ$*ꢂ%$ꢅꢁ)ꢅꢁꢅ#ꢉꢁ$)ꢅꢇ%(ꢅ*ꢄꢉꢅ)%&ꢄꢂ)*ꢂꢃꢁ*ꢉꢊꢅ
ꢂ$*ꢉꢍ(ꢁ*ꢂ%$ꢅ %ꢇꢅ ꢃꢁ*ꢁ"/*ꢂꢃꢅ )/)*ꢉ#)ꢅ *%ꢅ (ꢉꢁ"ꢂ0ꢉꢅ )*ꢉ&6ꢉꢃ%$%#/3:B;ꢅ
ꢓ))ꢂ)*ꢉꢊꢅ*ꢁ$ꢊꢉ#ꢅꢃꢁ*ꢁ"/)ꢂ)ꢅꢂ$,%",ꢉ)ꢅ*ꢄꢉꢅꢃ%$*(%""ꢉꢊꢅ*(ꢁ$)ꢂ*ꢂ%$ꢅ%ꢇꢅ%$ꢉꢅ
ꢃꢁ*ꢁ"/*ꢂꢃꢅ ꢃ/ꢃ"ꢉꢅ *%ꢅ *ꢄꢉꢅ %*ꢄꢉ()ꢅ ꢌ/ꢅ *ꢄꢉꢅ ꢂ$ꢅ )ꢂ*+ꢅ *(ꢁ$)ꢇ%(#ꢁ*ꢂ%$ꢅ %ꢇꢅ ꢁꢅ
ꢃꢁ*ꢁ"/)*ꢅ -ꢂ*ꢄꢅ ꢁ$ꢅ ꢉ.*ꢉ($ꢁ"ꢅ )*ꢂ#+"+)2ꢅ )+ꢃꢄꢅ ꢁ)ꢅ *ꢄꢉꢅ ꢁꢊꢊꢂ*ꢂ%$ꢅ %ꢇꢅ ꢁꢅ
(ꢉꢁꢍꢉ$*ꢅ ꢁ)ꢅ ꢁꢅ *(ꢂꢍꢍꢉ(3ꢅ ꢓ)ꢅ ꢁꢅ (ꢉ&(ꢉ)ꢉ$*ꢁ*ꢂ,ꢉꢅ ꢉ.ꢁ#&"ꢉꢅ %ꢇꢅ ꢁ))ꢂ)*ꢉꢊꢅ
*ꢁ$ꢊꢉ#ꢅ ꢃꢁ*ꢁ"/)ꢂ)2ꢅ ꢔ(+ꢌꢌ)ꢅ ꢊꢉ,ꢉ"%&ꢉꢊꢅ ꢁꢅ ꢕ+6ꢃꢁ*ꢁ"/0ꢉꢊꢅ (ꢂ$ꢍ6ꢃ"%)ꢂ$ꢍꢅ
#ꢉ*ꢁ*ꢄꢉ)ꢂ)5ꢄ/ꢊ(%ꢍꢉ$ꢁ*ꢂ%$ꢅ)ꢉ'+ꢉ$ꢃꢉꢅꢁꢃꢃ%#&ꢁ$ꢂꢉꢊꢅꢌ/ꢅ*ꢄꢉꢅ)ꢄꢂꢇ*ꢂ$ꢍꢅ
%ꢇꢅ ꢃꢁ*ꢁ"/*ꢂꢃꢅ ꢃ/ꢃ"ꢉ)ꢅ -ꢂ*ꢄꢅ *ꢄꢉꢅ ꢁ))ꢂ)*ꢁ$ꢃꢉꢅ %ꢇꢅ #%"ꢉꢃ+"ꢁ(ꢅ ꢄ/ꢊ(%ꢍꢉ$3:C;ꢅ
ꢓ"*ꢄ%+ꢍꢄꢅꢁꢅ$+#ꢌꢉ(ꢅ%ꢇꢅꢕ+6#ꢉꢊꢂꢁ*ꢉꢊꢅ*ꢁ$ꢊꢉ#ꢅꢃꢁ*ꢁ"/)ꢂ):C;ꢅꢄꢁ,ꢉꢅꢌꢉꢉ$ꢅ
(ꢉ&%(*ꢉꢊ2ꢅ*ꢄꢉꢅ(ꢉ&%(*ꢅꢌ/ꢅꢖ+)ꢃꢁꢅꢁ$ꢊꢅꢗ(ꢉ)*ꢁ*ꢅꢂ)ꢅ*ꢄꢉꢅ%$"/ꢅꢉ.ꢁ#&"ꢉꢅ%ꢇꢅ
ꢎ+6#ꢉꢊꢂꢁ*ꢉꢊꢅꢁ))ꢂ)*ꢉꢊꢅ*ꢁ$ꢊꢉ#ꢅꢃꢁ*ꢁ"/)ꢂ)ꢅ*%ꢅ*ꢄꢉꢅꢌꢉ)*ꢅ%ꢇꢅ*ꢄꢉꢅꢁ+*ꢄ%()4ꢅ
!$%-"ꢉꢊꢍꢉ3:D;ꢅ ꢋꢄ+)2ꢅ *ꢄꢉ(ꢉꢅ ꢂ)ꢅ (%%#ꢅ ꢇ%(ꢅ *ꢄꢉꢅ ꢊꢉ,ꢉ"%&#ꢉ$*ꢅ %ꢇꢅ $ꢉ-ꢅ
ꢃꢁ*ꢁ"/*ꢂꢃꢅ )/)*ꢉ#)3ꢅ ꢘ$ꢅ *ꢄꢂ)ꢅ )*+ꢊ/2ꢅ -ꢉꢅ ꢃꢄ%)ꢉꢅ *ꢄꢉꢅ ꢊ%+ꢌ"ꢉꢅ
ꢇ+$ꢃ*ꢂ%$ꢁ"ꢂ0ꢁ*ꢂ%$ꢅ%ꢇꢅ%"ꢉꢇꢂ$)ꢅ*ꢄ(%+ꢍꢄꢅꢁ0ꢂ(ꢂꢊꢂ$ꢉ)ꢅꢁ)ꢅꢁꢅ#%ꢊꢉ"ꢅ(ꢉꢁꢃ*ꢂ%$ꢅ
ꢁ$ꢊꢅ ꢊꢉ,ꢉ"%&ꢉꢊꢅ ꢁꢅ ꢎ+6#ꢉꢊꢂꢁ*ꢉꢊꢅ ꢁ))ꢂ)*ꢉꢊꢅ *ꢁ$ꢊꢉ#ꢅ ꢃꢁ*ꢁ"/)ꢂ)ꢅ &(%ꢃꢉ))ꢅ
ꢌ/ꢅ*+$ꢂ$ꢍꢅ*ꢄꢉꢅꢎ+ꢅꢃꢁ*ꢁ"/)*ꢅ-ꢂ*ꢄꢅ*ꢄꢉꢅꢁ))ꢂ)*ꢁ$ꢃꢉꢅ%ꢇꢅꢁ$ꢅ%.ꢂꢊꢁ$*3ꢅ
ꢀ
ꢈꢀ
ꢕꢀ
ꢅ3ꢋꢀ
ꢀꢀ
ꢕꢖꢀ
ꢕꢖꢀ
ꢏꢀ
ꢙꢀ
ꢅ3ꢋꢀ
ꢗ'ꢋꢊꢒꢘ"ꢌꢕꢀ
ꢊꢛꢜꢖꢌꢕꢇꢕꢒꢏꢀ
ꢊꢛꢜꢖꢌꢕꢇꢕꢒꢏꢀ
ꢊꢛꢜꢖꢌꢕꢇꢕꢒꢏꢀ
ꢊꢛꢜꢖꢌꢕꢇꢕꢒꢏꢀ
ꢊꢛꢜꢖꢌꢕꢇꢕꢒꢏꢀ
ꢊꢛꢜꢖꢌꢕꢇꢕꢒꢏꢀ
ꢊꢛꢜꢖꢌꢕꢇꢕꢒꢏꢀ
ꢀꢀ
ꢚꢀ
ꢅ3ꢋꢀ
ꢈꢉ ꢀ
ꢈꢉꢝꢀ
ꢈꢉꢝꢀ
ꢈ ꢀ
ꢃꢕꢀ
ꢙ ꢀ
ꢙꢕꢀ
ꢏꢏꢀ
ꢙꢕꢀ
ꢏꢝꢀ
ꢎꢀ
ꢖꢀ
ꢅ3ꢊ.70ꢌꢖꢊꢒꢁ%ꢌꢕꢀ
ꢅ3ꢊ.70ꢌꢖꢊꢒꢁ%ꢌꢕꢀ
ꢅ3ꢊ.70ꢌꢖꢊꢒꢁ%ꢌꢕꢀ
ꢅ3ꢊ.70ꢌꢖꢊꢒꢁ%ꢌꢕꢀ
ꢅ3ꢊ.70ꢌꢖꢊꢒꢁ%ꢌꢕꢀ
ꢅ3ꢊ.70ꢌꢖꢊꢒꢁ%ꢌꢕꢀ
ꢅ3ꢊ.70ꢌꢖꢊꢒꢁ%ꢌꢕꢀ
ꢝꢂ"ꢄ
ꢀ
ꢀ
ꢃꢂ#ꢄ
ꢎꢂ$ꢄꢀ
ꢏꢂ%ꢄꢀ
ꢈꢉꢝꢀ
ꢈꢉꢝꢀ
ꢕꢖꢀ
ꢙꢂ&ꢄ
ꢀ
ꢈ ꢀ
ꢕꢖꢀ
ꢙꢀ
:ꢁ;ꢅ@??ꢅ#ꢍ5@3?ꢅ##%"ꢅ%ꢇꢅ*ꢄꢉꢅ)*ꢁ(*ꢂ$ꢍꢅ#ꢁ*ꢉ(ꢂꢁ")ꢅ-ꢉ(ꢉꢅ+)ꢉꢊ3ꢅ:ꢌ;ꢅꢘ)%"ꢁ*ꢉꢊꢅ/ꢂꢉ"ꢊꢅꢅ
:ꢃ;ꢅꢅD?ꢅ#%"Jꢅ8ꢏ C9AꢐAꢑFꢅ-ꢁ)ꢅ+)ꢉꢊ3ꢅ:ꢊ;ꢅADꢅ#%"Jꢅ8ꢏ C9AꢐAꢑFꢅ-ꢁ)ꢅ+)ꢉꢊ3ꢅ:ꢉ;ꢅ@ꢅ#%"Jꢅ%ꢇꢅ
ꢎ+8&/(9C8ꢑꢋꢇ9Aꢅꢁ$ꢊꢅD?ꢅ#%"Jꢅ%ꢇꢅ8ꢏ C9AꢐAꢑFꢅ-ꢉ(ꢉꢅ+)ꢉꢊ3ꢅ:ꢇ;ꢅ@ꢅ#%"Jꢅ%ꢇꢅꢎ+8&/(9C8ꢑꢋꢇ9A2ꢅ
D?ꢅ#%"Jꢅ%ꢇꢅ8ꢏ C9AꢐAꢑF2ꢅꢁ$ꢊꢅADꢅꢉ'+ꢂ,ꢅ%ꢇꢅꢚꢉꢑ ꢅ-ꢉ(ꢉꢅ+)ꢉꢊ3ꢅ:ꢍ;ꢅ@ꢅ#%"Jꢅ%ꢇꢅ
ꢎ+8&/(9C8ꢑꢋꢇ9Aꢅꢁ$ꢊꢅD?ꢅ#%"Jꢅ%ꢇꢅ8ꢏ C9AꢐAꢑFꢅ-ꢉ(ꢉꢅ+)ꢉꢊꢅꢁ$ꢊꢅ)ꢉꢃ%$ꢊꢅ)*ꢉ&ꢅ-ꢁ)ꢅ
ꢃ%$ꢊ+ꢃ*ꢉꢊꢅꢁ*ꢅ(%%#ꢅ*ꢉ#&ꢉ(ꢁ*+(ꢉ3ꢅ
ꢅ
ꢐꢍꢑꢆꢌꢂꢑꢉ ꢁꢅꢉꢒꢈꢑꢇꢆꢑꢑꢈꢄꢁꢉ
ꢉ
ꢎꢈꢚꢄꢔꢄꢅꢛꢙꢅꢙ%(!ꢂ$ꢍꢅꢄ/&%*ꢄꢉ)ꢂ)ꢅ%ꢇꢅꢎ+6ꢁ))ꢂ)*ꢉꢊꢅ*ꢁ$ꢊꢉ#ꢅꢃꢁ*ꢁ"/)ꢂ)ꢅ
low
Lewis acidity
Cu(I)
high
Lewis acidity
Cu(II or III)+
Nu–
ꢓ*ꢅ *ꢄꢉꢅ %+*)ꢉ*ꢅ %ꢇꢅ *ꢄꢉꢅ (ꢉ)ꢉꢁ(ꢃꢄ2ꢅ -ꢉꢅ *ꢉ)*ꢉꢊꢅ %+(ꢅ ꢄ/&%*ꢄꢉ)ꢂ)ꢅ
+)ꢂ$ꢍꢅ )*/(ꢉ$ꢉꢅ ꢁ)ꢅ ꢁꢅ #%ꢊꢉ"ꢅ )+ꢌ)*(ꢁ*ꢉꢅ 8ꢋꢁꢌ"ꢉꢅ @93ꢅ ꢛꢂ()*2ꢅ )*/(ꢉ$ꢉꢅ
ꢛꢋ9ꢅ-ꢁ)ꢅ)+ꢌ ꢉꢃ*ꢉꢊꢅ*%ꢅ*ꢄꢉꢅ)*ꢁ$ꢊꢁ(ꢊꢅꢁ0ꢂ(ꢂꢊꢂ$ꢁ*ꢂ%$ꢅꢃ%$ꢊꢂ*ꢂ%$):G;ꢅ
-ꢂ*ꢄꢅꢗꢄꢘKꢏꢋ)ꢅ8@3?ꢅꢉ'+ꢂ,92ꢅꢎ+ꢘꢅ8Dꢅ#%"J9ꢅꢁ$ꢊꢅꢚꢐCꢜꢅꢂ$ꢅꢚꢉꢎꢏꢅꢁ*ꢅ
ꢁ#ꢌꢂꢉ$*ꢅ*ꢉ#&ꢉ(ꢁ*+(ꢉꢅ*%ꢅꢇ%(#ꢅ*ꢄꢉꢅꢊꢉ)ꢂ(ꢉꢊꢅꢁ0ꢂ(ꢂꢊꢂ$ꢉꢅꢜꢋꢅꢂ$ꢅE?Jꢅ
/ꢂꢉ"ꢊ3:@?;ꢅ ꢓꢇ*ꢉ(ꢅ ꢁꢊꢊꢂ*ꢂ%$ꢅ %ꢇꢅ ꢁ$ꢅ ꢉ.ꢃꢉ))ꢅ %ꢇꢅꢚꢉꢑ ꢅ8D?ꢅ ꢉ'+ꢂ,9ꢅ*%ꢅ
oxidant
8
R2
R2
R1 R2
NR
R3
R3
NHR
R1
R1
Nu
R
3 R4
R4
R4
nucleophilic
ring opening
aziridination
ꢅ
ꢀ
*ꢄꢉꢅ (ꢉꢁꢃ*ꢂ%$ꢅ #ꢂ.*+(ꢉ2ꢅ *ꢄꢉꢅ /ꢂꢉ"ꢊꢅ %ꢇꢅ *ꢄꢉꢅ ꢉ.&ꢉꢃ*ꢉꢊꢅ &(%ꢊ+ꢃ*ꢅ ꢝꢋ
ꢅ
ꢁ'$ꢀ 5-0)(,&ꢀ '7.-2'$1(1ꢀ %-0ꢀ 2'$ꢀ #-3!*$ꢀ %3,"2(-, *(8 2(-,ꢀ -%ꢀ
-ꢁ)ꢅꢇ%(#ꢉꢊꢅꢂ$ꢅ%$"/ꢅFJꢅ-ꢂ*ꢄꢅ(ꢉꢃ%,ꢉ(/ꢅ%ꢇꢅ@FJꢅ%ꢇꢅꢜꢋ2ꢅꢂ$ꢊꢂꢃꢁ*ꢂ$ꢍꢅ
*ꢄꢁ*ꢅ *ꢄꢉꢅ ꢂ$ꢂ*ꢂꢁ""/ꢅ ꢁꢊꢊꢉꢊꢅ ꢎ+ꢅ ꢃꢁ*ꢁ"/)*ꢅ -ꢁ)ꢅ $%*ꢅ ꢉꢇꢇꢉꢃ*ꢂ,ꢉꢅ ꢇ%(ꢅ
&(%#%*ꢂ$ꢍꢅ *ꢄꢉꢅ (ꢂ$ꢍ6%&ꢉ$ꢂ$ꢍꢅ (ꢉꢁꢃ*ꢂ%$3ꢅ ꢙꢉꢅ *ꢄꢉ$ꢅ ꢁꢊꢊꢉꢊꢅ ꢁ$ꢅ
%.ꢂꢊꢁ$*ꢅ ꢁ)ꢅ ꢁꢅ *(ꢂꢍꢍꢉ(ꢅ *%ꢅ ꢃ%$,ꢉ(*ꢅ *ꢄꢉꢅ ꢎ+6ꢃꢁ*ꢁ"/)*ꢅ *%ꢅ )*(%$ꢍꢉ(ꢅ
ꢝꢉ-ꢂ)ꢅ ꢁꢃꢂꢊꢂꢃꢅ )&ꢉꢃꢂꢉ)ꢅ *%ꢅ &(%#%*ꢉꢅ *ꢄꢉꢅ (ꢂ$ꢍ6%&ꢉ$ꢂ$ꢍꢅ (ꢉꢁꢃ*ꢂ%$ꢅ
8ꢉ$*(ꢂꢉ)ꢅ Aꢅ ꢁ$ꢊꢅ B93ꢅ ꢘ$ꢅ ꢃ%$*(ꢁ)*ꢅ *%ꢅ ꢗꢄꢘ8ꢑꢓꢃ9A2ꢅ 8ꢏ C9AꢐAꢑFꢅ -ꢁ)ꢅ
ꢉꢇꢇꢉꢃ*ꢂ,ꢉꢅꢇ%(ꢅ*ꢄꢉꢅ)#%%*ꢄꢅꢁ$ꢊꢅꢃ%#&"ꢉ*ꢉꢅꢃ%$)+#&*ꢂ%$ꢅ%ꢇꢅ*ꢄꢉꢅ
ꢁ0ꢂ(ꢂꢊꢂ$ꢉꢅ ꢂ$*ꢉ(#ꢉꢊꢂꢁ*ꢉꢅ *%ꢅ ꢍꢂ,ꢉꢅ *ꢄꢉꢅ ꢊꢉ)ꢂ(ꢉꢊꢅ &(%ꢊ+ꢃ*ꢅ ꢝꢋꢅ -ꢂ*ꢄꢅ
EAJꢅ /ꢂꢉ"ꢊ3:@@;ꢅ ꢓꢇ*ꢉ(ꢅ )ꢃ(ꢉꢉ$ꢂ$ꢍꢅ %ꢇꢅ ,ꢁ(ꢂ%+)ꢅ %.ꢂꢊꢁ$*)ꢅ ꢁ$ꢊꢅ ꢎ+6
ꢃꢁ*ꢁ"/)*)2:@A;ꢅꢎ+8&/(9C8ꢑꢋꢇ9A:@B;ꢅ&(%,ꢉꢊꢅ*%ꢅꢌꢉꢅ*ꢄꢉꢅ#%)*ꢅ)+ꢂ*ꢁꢌ"ꢉꢅ
8ꢉ$*(/ꢅC93ꢅꢏꢉ.*2ꢅꢂ$ꢅ*ꢄꢉꢅ)*+ꢊꢂꢉ)ꢅ%$ꢅ*ꢄꢉꢅꢁ#%+$*ꢅ%ꢇꢅ8ꢏ C9AꢐAꢑF2ꢅ
-ꢉꢅꢇ%+$ꢊꢅ*ꢄꢁ*ꢅ*ꢄꢉꢅꢁ0ꢂ(ꢂꢊꢂ$ꢉꢅ(ꢂ$ꢍꢅ%&ꢉ$ꢂ$ꢍꢅ&(%ꢃꢉꢉꢊꢉꢊꢅ)#%%*ꢄ"/ꢅ
-ꢂ*ꢄꢅ D?ꢅ #%"Jꢅ %ꢇꢅ 8ꢏ C9AꢐAꢑFꢅ 8ꢉ$*(/ꢅ D93ꢅ %-ꢉ,ꢉ(2ꢅ -ꢄꢉ$ꢅ ADꢅ
-*$%(,1ꢀ 2'0-3&'ꢀ 8(0(#(,$1ꢂꢃꢄꢀ !7ꢀ ꢀ ꢅ3ꢆ" 2 *78$#ꢀ 11(12$#ꢀ 2 ,#$+ꢀ
0$ "2(-,ꢀ!7ꢀ23,(,&ꢀ2'$ꢀꢅ3ꢀ" 2 *712ꢀ(1ꢀ#$.("2$#ꢀ(,ꢀꢇ"'$+$ꢀꢈꢉꢀꢁ'$ꢀ
"-,4$,2(-, *ꢀ ꢅ3ꢊꢋꢌꢆ" 2 *78$#ꢀ 8(0(#(, 2(-,ꢀ -%ꢀ -*$%(,1ꢀ 5(2'ꢀ ꢀ
,(20$,$ꢀ .0$"301-0ꢍꢂꢎꢄꢀ (,ꢀ 1(23ꢀ "-,4$01(-,ꢀ -%ꢀ 2'$ꢀ -6(# 2(-,ꢀ 12 2$ꢀ -%ꢀ
ꢂ ꢄꢀ
ꢀꢁ#ꢂ"#ꢃꢄꢁ0ꢁ.ꢂ"#ꢅꢃꢀ+ꢆꢃꢇ#+) .'#ꢃꢈꢉꢊꢁꢅꢃꢁ(ꢊꢃꢀ+ꢆꢃꢇ#ꢊꢉ-),"#ꢃꢋ)%.2ꢁ'ꢁꢃ
ꢌ+ꢁꢊ.ꢁ-ꢉꢃꢍꢂ"))&ꢃ) ꢃꢎ"ꢁ+'ꢁꢂ.ꢉ-#ꢂꢁ&ꢃꢍꢂ#ꢉ(ꢂꢉ,ꢅꢃꢋ)")%.ꢃꢈ(#/ꢉ+,#-2ꢃ
ꢏ)ꢐꢁꢃ ꢑꢒꢅꢃꢏ+ꢁ'ꢁ%#ꢅꢃꢏ)ꢐꢁꢑ%.ꢅꢃꢍꢉ(ꢊꢁ#ꢅꢃꢓ#2ꢁ!#ꢃꢔꢕꢖꢑꢕꢗꢘꢕꢅꢃꢙꢁ*ꢁ(ꢆꢃ
ꢚꢑ'ꢁ#&ꢛꢃ-)%.2ꢁ'ꢁꢜ'ꢁ#&ꢆ*"ꢁ+'ꢆ-)")%.ꢆꢁꢂꢆ$*ꢆꢃ
"--*ꢛꢝꢝ000ꢆ*"ꢁ+'ꢆ-)")%.ꢆꢁꢂꢆ$*ꢝ4,ꢉ#3).ꢝ#(ꢊꢉ1ꢆ"-'&ꢃ
ꢃ
ꢍ.**)+-#(!ꢃ#( )+'ꢁ-#)(ꢃ )+ꢃ-"#,ꢃꢁ+-#ꢂ&ꢉꢃ#,ꢃ!#/ꢉ(ꢃ/#ꢁꢃꢁꢃ&#(%ꢃꢁ-ꢃ-"ꢉꢃꢉ(ꢊꢃ) ꢃ
-"ꢉꢃꢊ)ꢂ.'ꢉ(-ꢆꢃ
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201900088
European Journal of Organic Chemistry
COMMUNICATION
ꢀꢁꢂCꢃ ꢁꢄꢃ 0ꢅꢆ;19ꢇ9ꢈ?ꢃ &ꢉ"ꢃ $"ꢊꢋ*ꢃ #ꢌꢊꢃ !ꢊꢉꢍ#ꢎꢁꢏꢃ #ꢎꢀꢊꢃ &ꢉ"ꢃ ꢋꢊ"ꢎ!ꢊꢋꢃ ꢐ!ꢁꢋ$ꢍ#ꢃ 0ꢁ1.ꢇꢌꢃ &ꢉ"ꢃ ꢄꢁ!ꢀꢊꢋꢃ ꢎꢏꢃ ꢑꢁꢁꢋꢃ (ꢎꢊꢂꢋꢃ 0?9C1ꢃ
ꢐ!ꢁꢂꢁꢏꢑꢊꢋꢃ 0ꢊꢏ#!(ꢃ =1+ꢃ ꢒꢄ#ꢊ!ꢃ ꢁꢐ#ꢎꢀꢎ)ꢎꢏꢑꢃ ꢁ#ꢌꢊ!ꢃ ꢍꢁꢏꢋꢎ#ꢎꢁꢏ"*ꢃ &ꢎ#ꢌꢁ$#ꢃꢂꢁ""ꢃꢁꢄꢃ#ꢌꢊꢃꢁꢐ#ꢎꢍꢉꢂꢃꢐ$!ꢎ#(ꢃ0ꢊꢏ#!(ꢃ81+ꢃꢈꢏꢃ#ꢌꢊꢃꢁ#ꢌꢊ!ꢃꢌꢉꢏꢋ*ꢃ
ꢎꢏꢍꢂ$ꢋꢎꢏꢑꢃ "ꢁꢂ%ꢊꢏ#"*ꢃ ꢏꢎ#!ꢊꢏꢊꢃ ꢐ!ꢊꢍ$!"ꢁ!"*ꢃ ꢉꢏꢋꢃ ꢍꢉ#ꢉꢂ(#ꢎꢍꢃ !ꢉꢍꢊꢀꢎꢍꢃ ꢇꢌꢃ &ꢉ"ꢃ ꢁꢓ#ꢉꢎꢏꢊꢋꢃ ꢎꢏꢃ #ꢌꢊꢃ ꢉꢓ"ꢊꢏꢍꢊꢃ ꢁꢄꢃ ꢔ$.ꢍꢉ#ꢉꢂ("#ꢃ ꢉ#ꢃ
ꢉꢀꢁ$ꢏ#"*28;3ꢃ &ꢊꢃ ꢊ"#ꢉꢓꢂꢎ"ꢌꢊꢋꢃ#ꢌꢊꢃ ꢍꢁꢏꢋꢎ#ꢎꢁꢏ"ꢃ $"ꢎꢏꢑꢃ 8ꢃ ꢀꢁꢂCꢃ ꢁꢄꢃ ?7ꢃ4ꢔꢃ0#ꢌꢊꢃ!ꢊꢉꢍ#ꢎꢁꢏꢃꢋꢎꢋꢏ,#ꢃꢐ!ꢁꢍꢊꢊꢋꢃꢉ#ꢃꢉꢂꢂꢃꢉ#ꢃ<7ꢃ4ꢔ1+ꢃ
ꢔ$0ꢐ(!1;0ꢈꢕꢄ19ꢃꢉꢏꢋꢃ<7ꢃꢀꢁꢂCꢃꢁꢄꢃ0ꢅꢆ;19ꢇ9ꢈ?ꢃꢎꢏꢃꢖꢊꢔꢅꢃ0ꢊꢏ#!ꢎꢊ"ꢃ>ꢃ
ꢆꢉ%ꢎꢏꢑꢃ ꢊ"#ꢉꢓꢂꢎ"ꢌꢊꢋꢃ #ꢌꢊꢃ ꢁꢐ#ꢎꢀꢉꢂꢃ ꢍꢁꢏꢋꢎ#ꢎꢁꢏ"*ꢃ &ꢊꢃ #ꢌꢊꢏꢃ
ꢉꢏꢋꢃ?1+ꢃꢗꢎꢏꢉꢂꢂ(*ꢃ&ꢊꢃꢄꢁ$ꢏꢋꢃ#ꢌꢉ#ꢃꢌꢊꢉ#ꢎꢏꢑꢃꢍꢁꢏꢋꢎ#ꢎꢁꢏ"ꢃꢉꢏꢋꢃꢉꢋꢋꢎ#ꢎꢁꢏꢃ ꢎꢏ%ꢊ"#ꢎꢑꢉ#ꢊꢋꢃ #ꢌꢊꢃ "ꢍꢁꢐꢊꢃ ꢁꢄꢃ #ꢌꢊꢃ "$ꢓ"#!ꢉ#ꢊ"ꢃ 0ꢇꢍꢌꢊꢀꢊꢃ 91+ꢃ ꢛꢎ#ꢌꢃ
ꢁꢄꢃ0ꢅꢆ;19ꢇ9ꢈ?ꢃꢉ"ꢃꢉꢏꢃꢁ'ꢎꢋꢉꢏ#ꢃ&ꢊ!ꢊꢃꢏꢊꢍꢊ""ꢉ!(ꢃ#ꢁꢃꢄꢉꢍꢎꢂꢎ#ꢉ#ꢊꢃ#ꢌꢊꢃ !ꢊꢑꢉ!ꢋꢃ#ꢁꢃ#ꢌꢊꢃ"$ꢂꢄꢁꢏ(ꢂꢃꢑ!ꢁ$ꢐꢃꢁꢏꢃ#ꢌꢊꢃꢏꢎ#!ꢁꢑꢊꢏ*ꢃꢂ.ꢅ"ꢃ0ꢍꢌ1ꢃꢉꢏꢋꢃꢃ.
"ꢊꢍꢁꢏꢋꢃ"#ꢊꢐꢃꢁꢄꢃꢃꢏ$ꢍꢂꢊꢁꢐꢌꢎꢂꢎꢍꢃ!ꢎꢏꢑꢃꢁꢐꢊꢏꢎꢏꢑꢃꢁꢄꢃꢉ)ꢎ!ꢎꢋꢎꢏꢊꢃ0ꢊꢏ#!ꢎꢊ"ꢃ ꢅ"ꢃ 0ꢎꢌ1ꢃ ꢑ!ꢁ$ꢐ"ꢃ &ꢊ!ꢊꢃ ꢉꢂ"ꢁꢃ"$ꢎ#ꢉꢓꢂꢊꢃꢄꢁ!ꢃ #ꢌꢊꢃ#ꢉꢏꢋꢊꢀꢃ !ꢊꢉꢍ#ꢎꢁꢏ+ꢃ
@ꢃꢉꢏꢋꢃ871+ꢃ
ꢇ$ꢓ"#ꢎ#$ꢊꢏ#"ꢃ ꢁꢏꢃ #ꢌꢊꢃ ꢓꢊꢏ)ꢊꢏꢊꢃ !ꢎꢏꢑꢃ ꢁꢄꢃ "#(!ꢊꢏꢊꢃ "ꢎꢑꢏꢎꢄꢎꢍꢉꢏ#ꢂ(ꢃ
ꢉꢄꢄꢊꢍ#ꢊꢋꢃ #ꢌꢊꢃ !ꢎꢏꢑ.ꢁꢐꢊꢏꢎꢏꢑꢃ "#ꢊꢐ+ꢃ ꢕꢌ$"*ꢃ #ꢌꢊꢃ ꢊꢂꢊꢍ#!ꢁꢏ.ꢋꢁꢏꢉ#ꢎꢏꢑꢃ
ꢀꢊ#ꢌꢁ'(ꢃ ꢑ!ꢁ$ꢐꢃ 0ꢇꢏ1ꢃ ꢄꢉꢍꢎꢂꢎ#ꢉ#ꢊꢋꢃ #ꢌꢊꢃ !ꢊꢉꢍ#ꢎꢁꢏ*ꢃ &ꢌꢊ!ꢊꢉ"ꢃ #ꢌꢊꢃ
!ꢊꢉꢍ#ꢎꢁꢏꢃ ꢁꢄꢃ #ꢌꢊꢃ "#(!ꢊꢏꢊꢃ ꢋꢊ!ꢎ%ꢉ#ꢎ%ꢊ"ꢃ ꢓꢊꢉ!ꢎꢏꢑꢃ ꢉꢏꢃ ꢊꢂꢊꢍ#!ꢁꢏ.
&ꢎ#ꢌꢋ!ꢉ&ꢎꢏꢑꢃꢑ!ꢁ$ꢐꢃꢁꢏꢃ#ꢌꢊꢃꢓꢊꢏ)ꢊꢏꢊꢃ!ꢎꢏꢑꢃ!ꢊ $ꢎ!ꢊꢋꢃꢐ!ꢁꢂꢁꢏꢑꢊꢋꢃ
#ꢌꢊꢃ !ꢊꢉꢍ#ꢎꢁꢏꢃ #ꢎꢀꢊꢃ ꢉꢏꢋꢃꢎꢏꢍ!ꢊꢉ"ꢊꢋꢃ #ꢌꢊꢃ ꢉꢀꢁ$ꢏ#ꢃ ꢁꢄꢃ ꢍꢉ#ꢉꢂ("#ꢃ0ꢇꢐꢄ
ꢀꢁꢂꢃꢄꢅꢆꢇꢀꢅ$ꢍꢂꢊꢁꢐꢌꢎꢂꢎꢍꢃ!ꢎꢏꢑꢃꢁꢐꢊꢏꢎꢏꢑꢃꢁꢄꢃꢁꢐ#ꢎꢍꢉꢂꢂ(ꢃꢉꢍ#ꢎ%ꢊꢃꢉ)ꢎ!ꢎꢋꢎꢏꢊꢃꢃ
Cu(pyr)4(OTf)2 (1 mol%)
(NH4)2S2O8 (50 mol%)
MeOH (50 eq)
OMe
NTs
NHTs
Ph
(R)-2a
Ph
MS4Å[a], MeCN (0.5 M)
Temp., Time
(S)-3a
ꢉꢏꢋꢃꢇꢑ1+ꢃꢕꢌꢊꢃ#ꢉꢏꢋꢊꢀꢃ!ꢊꢉꢍ#ꢎꢁꢏꢃꢉꢂ"ꢁꢃꢐ!ꢁꢍꢊꢊꢋꢊꢋꢃ&ꢌꢊꢏꢃ$"ꢎꢏꢑꢃ
ꢀꢊ#ꢌ(ꢂꢃ "#(!ꢊꢏꢊꢃ ꢉꢏꢋꢃ ꢍ(ꢍꢂꢎꢍꢃ ꢋꢊ!ꢎ%ꢉ#ꢎ%ꢊ"*ꢃ ꢏꢉꢀꢊꢂ(*ꢃ ꢎꢏꢋꢊꢏꢊꢃ ꢉꢏꢋꢃ
8*9.ꢋꢎꢌ(ꢋ!ꢁꢏꢉꢐꢌ#ꢌꢉꢂꢊꢏꢊ*ꢃꢉꢏꢋꢃ#ꢌꢊꢃꢋꢊ"ꢎ!ꢊꢋꢃꢐ!ꢁꢋ$ꢍ#"ꢃ0 *ꢃꢇꢈꢃꢉꢏꢋꢃ
α.
ꢀ
ꢁ)-,/ꢀ
ꢊꢀ
ꢂ.ꢀ!ꢃ-ꢄꢀ
ꢅ#(+ꢄꢀꢆ0ꢂꢇꢀ
ꢅ&(#ꢀꢆ%ꢇꢀ
ꢎꢄꢌꢀ
ꢈ&#'"ꢀꢆꢉꢇꢆ ꢇ
ꢏꢎꢀ
ꢀ
##ꢀꢆꢉꢇꢆ!ꢇ
ꢀ
ꢇ
ꢇꢉ1ꢃꢄꢁ!ꢀꢊꢋꢃꢓ(ꢃ#ꢌꢊꢃ!ꢊꢑꢎꢁ"ꢊꢂꢊꢍ#ꢎ%ꢊꢃ!ꢎꢏꢑ.ꢁꢐꢊꢏꢎꢏꢑꢃꢉ#ꢃ#ꢌꢊꢃꢓꢊꢏ)(ꢂꢎꢍꢃ
ꢐꢁ"ꢎ#ꢎꢁꢏꢃ &ꢊ!ꢊꢃ ꢁꢓ#ꢉꢎꢏꢊꢋꢃ ꢎꢏꢃ ꢀꢁꢋꢊ!ꢉ#ꢊꢃ #ꢁꢃ ꢌꢎꢑꢌꢃ (ꢎꢊꢂꢋ"+ꢃ ꢘꢏꢃ #ꢌꢊꢃ
ꢍꢉ"ꢊꢃ ꢁꢄꢃ ꢀꢊ#ꢌ(ꢂꢃ ꢍꢎꢏꢏꢉꢀꢉ#ꢊ*ꢃ #ꢌꢊꢃ (ꢎꢊꢂꢋꢃ ꢄ!ꢁꢀꢃ ꢚꢌꢘDꢅꢕ"ꢃ &ꢉ"ꢃ
ꢀꢁꢋꢊ!ꢉ#ꢊꢃ ꢓꢊꢍꢉ$"ꢊꢃ ꢁꢄꢃ #ꢌꢊꢃ ꢂꢁ&ꢃ !ꢊꢉꢍ#ꢎ%ꢎ#(ꢃ ꢎꢏꢃ #ꢌꢊꢃ ꢉ)ꢎ!ꢎꢋꢎꢏꢉ#ꢎꢁꢏꢃ
"#ꢊꢐ+28=3ꢃ
ꢋꢀ
ꢌꢍꢀ
ꢏꢍꢀ
ꢐꢑꢑꢀ
ꢎꢀ
ꢀꢀ
ꢊꢄꢍꢀ
ꢒꢍꢀ
ꢓꢄꢌꢀ
2ꢉ3ꢃ877ꢃꢀꢑ-8+7ꢃꢀꢀꢁꢂꢃꢁꢄꢃ#ꢌꢊꢃ"#ꢉ!#ꢎꢏꢑꢃꢀꢉ#ꢊ!ꢎꢉꢂ"ꢃ&ꢊ!ꢊꢃ$"ꢊꢋ+ꢃ2ꢓ3ꢃꢘ"ꢁꢂꢉ#ꢊꢋꢃ(ꢎꢊꢂꢋꢃꢃ
2ꢍ3ꢃꢜꢏꢉꢏ#ꢎꢁꢀꢊ!ꢎꢍꢃꢊ'ꢍꢊ""ꢃ&ꢉ"ꢃꢋꢊ#ꢊ!ꢀꢎꢏꢊꢋꢃꢓ(ꢃꢍꢌꢎ!ꢉꢂꢃꢆꢚ ꢔꢃꢉꢏꢉꢂ("ꢎ"+ꢃꢃ
ꢃ
ꢀꢁꢂꢃꢄꢅꢈꢇꢀꢇꢍꢁꢐꢊꢃꢁꢄꢃꢁ'(ꢑꢊꢏꢃꢏ$ꢍꢂꢊꢁꢐꢌꢎꢂꢊ"ꢃ
ꢀꢁ ꢂꢃꢂꢄꢅꢆꢃꢇꢍꢁꢐꢊꢃꢁꢄꢃ"$ꢓ"#!ꢉ#ꢊ"
ꢃ
Cu(pyr)4(OTf)2 (1 mol%)
PhI=NP (1.0 eq)
MS4Å[a]
(NH4)2S2O8
(50 mol%)
MeOH (50 eq)
(NH4)2S2O8
(Y mol%)
ROH (25 eq)
Cu(pyr)4(OTf)2 (X mol%)
PhI=NTs (1.0 eq)
MS4Å[a]
R1
MeO
Ar
R1
OR
NHTs
R2
Ph
1a
NHTs
MeCN (0.5 M)
rt, 24 h;
50 °C, time
50 °C, Time
Ph
Ar
MeCN (0.5 M)
rt, 24 h;
R2
3a-13a
ꢀ
3a-3k, 4a, 5a
1a-1k
OMe
OMe
OMe
ꢖꢀ
ꢆ(*'ꢉꢇꢀ
ꢈꢀ
ꢆ(*'ꢉꢇꢀ
ꢅ&(#ꢀ
ꢆ%ꢇꢀ
ꢈ&#'"ꢀ
ꢁ)-,/ꢀ
ꢔꢀꢕꢀ
ꢆꢉꢇꢆ ꢇ
ꢏꢌꢀ
ꢏꢎꢀ
ꢒꢚꢀ
ꢚꢎꢀ
ꢏꢌꢀ
ꢏꢍꢀ
ꢏꢊꢀ
ꢒꢍꢀ
ꢚꢍꢀ
ꢀ
NHTs
NHo-Ns
NHp-Ns
ꢊꢀ
ꢎꢀ
ꢆ!ꢇꢀ
ꢗ#ꢀꢈꢁꢀ
ꢁ-ꢀꢉꢁꢀ
ꢊꢀ
ꢊꢀ
ꢌꢀ
ꢌꢀ
ꢊꢀ
ꢊꢀ
ꢊꢀ
ꢊꢀ
ꢌꢀ
ꢌꢍꢀ
ꢌꢍꢀ
ꢊꢄꢌꢀ
ꢎꢄꢍꢀ
ꢎꢄꢌꢀ
ꢎꢄꢌꢀ
ꢎꢄꢍꢀ
ꢊꢄꢍꢀ
ꢎꢄꢍꢀ
ꢊꢄꢍꢀ
ꢊꢄꢌꢀ
3a
4a
1.0 h, 50%[b]
5a
2.0 h, 92%[b]
2.0 h, 59%[b]
OMe
OMe
OMe
NHTs
NHTs
NHTs
ꢀꢘꢙ,ꢀ ꢁꢀ
ꢁꢂꢛ.ꢀꢊꢁꢀ
ꢛ)ꢀꢋꢁꢀ
ꢊꢍꢍꢀ
ꢊꢍꢍꢀ
ꢌꢍꢀ
MeO
Me
Br
3b
3c
3d
ꢓꢆ!ꢇ
ꢀ
0.5 h, 92%[b]
1.0 h, 93%[b]
4.0 h, 92%[b]
OMe
OMe
OMe
ꢌꢀ
NHTs
NHTs
NHTs
ꢚꢀ
ꢙ,*+ꢃ,$/'ꢀꢌꢍꢁꢀ
ꢜ''/'ꢀꢌꢌꢁꢀ
ꢜ!ꢀꢌꢆꢁꢀ
ꢌꢍꢀ
O2N
Br
3e
NC
3g
3f
11 h, 84%[b], [d]
ꢒꢀ
ꢌꢍꢀ
3.5 h, 94%[b], [c]
15 h, 80%[b], [d]
OMe
OMe
MeO Me
NHTs
OMe
NHTs
ꢏꢀ
ꢌꢍꢀ
NHTs
CO2Me
ꢑꢆ!ꢇ
ꢀ
ꢝꢀꢌꢈꢁꢀ
ꢊꢍꢍꢀ
NHTs
3j
3h
3i
1.0 h, 47%[b], [e]
3k
0.5 h, 88%[b]
12 h, 44%[b], [e], [f]
2.5 h, 59%[b], [e]
ꢆꢃꢇꢀ877ꢃꢀꢑ-8+7ꢃꢀꢀꢁꢂꢃꢁꢄꢃ#ꢌꢊꢃ"#ꢉ!#ꢎꢏꢑꢃꢀꢉ#ꢊ!ꢎꢉꢂ"ꢃ&ꢊ!ꢊꢃ$"ꢊꢋ+ꢀꢆ ꢇꢀꢘ"ꢁꢂꢉ#ꢊꢋꢃ(ꢎꢊꢂꢋꢃꢃ
ꢆ!ꢇꢃꢕꢌꢊꢃ"ꢊꢍꢁꢏꢋꢃ"#ꢊꢐꢃ&ꢉ"ꢃꢐꢊ!ꢄꢁ!ꢀꢊꢋꢃꢉ#ꢃ!ꢊꢄꢂ$'+ꢃ
ꢃ
2ꢉ3ꢃ877ꢃꢀꢑ-8+7ꢃꢀꢀꢁꢂꢃꢁꢄꢃ#ꢌꢊꢃ"#ꢉ!#ꢎꢏꢑꢃꢀꢉ#ꢊ!ꢎꢉꢂ"ꢃ&ꢊ!ꢊꢃ$"ꢊꢋ+ꢃ2ꢓ3ꢃꢘ"ꢁꢂꢉ#ꢊꢋꢃ(ꢎꢊꢂꢋꢃ2ꢍ3ꢃ
ꢕꢌꢊꢃ"ꢊꢍꢁꢏꢋꢃ"#ꢊꢐꢃ&ꢉ"ꢃꢐꢊ!ꢄꢁ!ꢀꢊꢋꢃꢉ#ꢃ!ꢊꢄꢂ$'+ꢃ2ꢋ3ꢃꢕꢌꢊꢃ"ꢊꢍꢁꢏꢋꢃ"#ꢊꢐꢃ&ꢉ"ꢃꢐꢊ!ꢄꢁ!ꢀꢊꢋꢃ
ꢉ#ꢃ!ꢊꢄꢂ$'*ꢃꢉꢏꢋꢃꢔ$0ꢐ(!1;0ꢈꢕꢄ19ꢃ0<ꢃꢀꢁꢂC1ꢃꢉꢏꢋꢃ0ꢅꢆ;19ꢇ9ꢈ?ꢃ08+7ꢃꢊ $ꢎ%1ꢃ&ꢊ!ꢊꢃ$"ꢊꢋ+ꢃ2ꢊ3ꢃ
ꢇꢎꢏꢑꢂꢊꢃ ꢎ"ꢁꢀꢊ!ꢃ &ꢉ"ꢃ ꢁꢓ#ꢉꢎꢏꢊꢋ+ꢃ ꢇ#!$ꢍ#$!ꢉꢂꢃ ꢋꢊ#ꢊ!ꢀꢎꢏꢉ#ꢎꢁꢏꢃ ꢁꢄꢃ ꢇꢈꢃ ꢉꢏꢋꢃ ꢇꢉꢃ &ꢉ"ꢃ
ꢍꢁꢏꢋ$ꢍ#ꢊꢋꢃꢓ(ꢃꢋꢊ!ꢎ%ꢉ#ꢎ)ꢉ#ꢎꢁꢏꢃꢁꢄꢃꢙꢏꢁ&ꢏꢃꢍꢁꢀꢐꢁ$ꢏꢋ"+28>3ꢃ2ꢄ3ꢃꢈꢂꢊꢄꢎꢏꢃ0ꢊꢋ1ꢃ0<+7ꢃꢊ $ꢎ%1ꢃ
&ꢉ"ꢃ$"ꢊꢋ*ꢃꢉꢏꢋꢃ#ꢌꢊꢃ(ꢎꢊꢂꢋꢃ&ꢉ"ꢃꢓꢉ"ꢊꢋꢃꢁꢏꢃꢚꢌꢘDꢅꢕ"+ꢃ
ꢄ
ꢃ
ꢕꢌꢊꢃ #ꢉꢏꢋꢊꢀꢃ ꢍꢉ#ꢉꢂ(#ꢎꢍꢃ !ꢊꢉꢍ#ꢎꢁꢏꢃ &ꢉ"ꢃ ꢄꢊꢉ"ꢎꢓꢂꢊꢃ ꢄꢁ!ꢃ ꢉꢃ ꢓ!ꢁꢉꢋꢃ
!ꢉꢏꢑꢊꢃꢁꢄꢃꢁ'(ꢑꢊꢏꢃꢏ$ꢍꢂꢊꢁꢐꢌꢎꢂꢊ"ꢃ0ꢕꢉꢓꢂꢊꢃ:1+ꢃꢕꢌꢊꢃꢋꢊ"ꢎ!ꢊꢋꢃꢐ!ꢁꢋ$ꢍ#"ꢃ
&ꢊ!ꢊꢃ ꢁꢓ#ꢉꢎꢏꢊꢋꢃ $"ꢎꢏꢑꢃ %ꢉ!ꢎꢁ$"ꢃ ꢉꢂꢍꢁꢌꢁꢂ"*ꢃꢎꢏꢍꢂ$ꢋꢎꢏꢑꢃ ꢐ!ꢎꢀꢉ!(ꢃ0ꢇꢌ
ꢉꢏꢋꢃ ꢒꢌ1*ꢃ"ꢊꢍꢁꢏꢋꢉ!(ꢃ 0ꢓꢌ1*ꢃ#ꢊ!#ꢎꢉ!(ꢃ0ꢔꢌ1*ꢃꢓꢊꢏ)(ꢂꢃ0ꢕꢌ1*ꢃꢐ!ꢁꢐꢉ!ꢑ(ꢂꢃ
ꢊꢖꢌ1*ꢃ ꢉꢏꢋꢃ ꢉꢂꢂ(ꢂꢃ ꢉꢂꢍꢁꢌꢁꢂ"ꢃ 0ꢊꢊꢌ1ꢃ ꢎꢏꢃ ꢑꢁꢁꢋꢃ #ꢁꢃ ꢊ'ꢍꢊꢂꢂꢊꢏ#ꢃ (ꢎꢊꢂꢋ"ꢃ
0ꢊꢏ#!ꢎꢊ"ꢃ8/>1+ꢃꢘꢏꢃ#ꢌꢊꢃꢍꢉ"ꢊꢃꢁꢄꢃ"ꢊꢍꢁꢏꢋꢉ!(ꢃꢉꢏꢋꢃ#ꢊ!#ꢎꢉ!(ꢃꢉꢂꢍꢁꢌꢁꢂ"*ꢃ
ꢎꢏꢍ!ꢊꢉ"ꢊꢋꢃ ꢍꢉ#ꢉꢂ(#ꢎꢍꢃ ꢂꢁꢉꢋꢎꢏꢑꢃ ꢉꢏꢋꢃ !ꢊꢄꢂ$'ꢃ ꢍꢁꢏꢋꢎ#ꢎꢁꢏ"ꢃ &ꢊ!ꢊꢃ
!ꢊ $ꢎ!ꢊꢋꢃ ꢄꢁ!ꢃ #ꢌꢊꢃ !ꢎꢏꢑ.ꢁꢐꢊꢏꢎꢏꢑꢃ ꢐ!ꢁꢍꢊ""ꢃ 0ꢊꢏ#!ꢎꢊ"ꢃ :ꢃ ꢉꢏꢋꢃ ;1+ꢃ
ꢃ
ꢃ
ꢛꢊꢃ ꢍꢁꢏꢄꢎ!ꢀꢊꢋꢃ #ꢌꢉ#ꢃ ꢏ$ꢍꢂꢊꢁꢐꢌꢎꢂꢎꢍꢃ !ꢎꢏꢑꢃ ꢁꢐꢊꢏꢎꢏꢑꢃ ꢁꢄꢃ ꢉ)ꢎ!ꢎꢋꢎꢏꢊꢃ
%ꢎꢉꢃ ꢏꢁ#ꢃ ꢇꢅ8ꢃ ꢀꢊꢍꢌꢉꢏꢎ"ꢀꢃ ꢁ!ꢃ ꢇꢜꢕꢃ ꢐ!ꢁꢍꢊ""ꢃ ꢉ"ꢃ ꢝꢉꢂꢂ(,"ꢃ ꢑ!ꢁ$ꢐꢃ
!ꢊꢐꢁ!#ꢊꢋꢃ ꢐꢊ!"$ꢂꢄꢉ#ꢊ.ꢀꢊꢋꢎꢉ#ꢊꢋꢃ ꢉ)ꢎ!ꢎꢋꢎꢏꢊꢃ ꢁꢐꢊꢏꢎꢏꢑꢃ &ꢎ#ꢌꢁ$#ꢃ ꢔ$.
ꢍꢉ#ꢉꢂ("#"28<3ꢃꢓ$#ꢃꢇꢅ9ꢃꢀꢊꢍꢌꢉꢏꢎ"ꢀꢃ&ꢎ#ꢌꢃꢁꢐ#ꢎꢍꢉꢂꢂ(ꢃꢉꢍ#ꢎ%ꢊꢃꢉ)ꢎ!ꢎꢋꢎꢏꢊꢃ
0ꢀ1.ꢅꢌꢃ 0ꢕꢉꢓꢂꢊꢃ 91+ꢃ ꢅꢉꢀꢊꢂ(*ꢃ ꢎꢏꢃ #ꢌꢊꢃ ꢁꢐ#ꢎꢀꢉꢂꢃ ꢍꢁꢏꢋꢎ#ꢎꢁꢏ"*ꢃ #ꢌꢊꢃ
0
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201900088
European Journal of Organic Chemistry
COMMUNICATION
ꢀ&#%ꢁꢂ#ꢃ #ꢂ,ꢄꢅꢆꢂ% )*ꢄ #ꢄꢁ*ꢇ# )*ꢈꢄꢉ# &!$ꢄꢆ &ꢈꢇꢄꢊꢂꢄꢋꢌ%# ꢇ&ꢆꢂꢇꢄ ꢀ&#%ꢁꢂ#,ꢄ
γ
1ꢄꢅꢌꢇꢄ
δ
1ꢈꢅꢆ% ꢌꢂ$ꢄ2ꢃꢀꢄꢅꢌꢇꢄꢃꢁ3ꢄ(ꢂ#ꢂꢄ ꢊ%ꢅꢋꢌꢂꢇꢄꢊ*ꢄ%ꢁꢂꢄ
ꢊ*ꢄꢆ ꢌꢇ&ꢆ%ꢋꢌꢉꢄ%ꢁꢂꢄ$ꢂꢆ ꢌꢇꢄ!# ꢆꢂ$$ꢄ(ꢋ%ꢁꢄꢅꢆꢂ%ꢋꢆꢄꢅꢆꢋꢇꢄ #ꢄ&ꢌꢇꢂ#ꢄ %ꢅꢌꢇꢂꢃꢄ ꢆꢅ%ꢅꢈ*%ꢋꢆꢄ #ꢂꢅꢆ%ꢋ ꢌꢄ ꢎꢄ %ꢁꢂꢄ ꢍꢔꢘ1!# %ꢂꢆ%ꢂꢇꢄ ꢆꢅ#ꢊ )*ꢈꢋꢆꢄ
ꢅ"&ꢂ &$ꢄꢆ ꢌꢇꢋ%ꢋ ꢌ$ꢄ2ꢀꢁꢂꢄꢅꢌꢇꢄꢀꢃꢂ3/ꢄ
ꢅꢆꢋꢇ$ꢄ ꢁꢃꢄꢅꢌꢇꢄꢁꢄ,ꢄ#ꢂ$!ꢂꢆ%ꢋ'ꢂꢈ*/4:85ꢄꢓ %ꢅꢊꢈ*,ꢄꢋꢃꢋꢇꢅ%ꢂꢄꢇꢂ#ꢋ'ꢅ%ꢋ'ꢂꢄ
ꢄ
ꢁꢉꢄ ꢉꢅ'ꢂꢄ ꢀ1ꢃꢂ%ꢁ )*ꢄ γ1ꢈꢅꢆ%ꢅꢃꢄ !# ꢇ&ꢆ%ꢄ ꢃꢃꢄ %ꢁ# &ꢉꢁꢄ $ꢂꢈꢂꢆ%ꢋ'ꢂꢄ
ꢀꢁꢂꢃꢄꢅꢆꢇꢀꢘꢆ !ꢂꢄ ꢎꢄ %ꢁꢂ#ꢄꢌ&ꢆꢈꢂ !ꢁꢋꢈꢂ$ꢄ
ꢌ&ꢆꢈꢂ !ꢁꢋꢈꢋꢆꢄ#ꢋꢌꢉ1 !ꢂꢌꢋꢌꢉꢄꢊ*ꢄ )ꢋꢃꢂꢄꢌꢋ%# ꢉꢂꢌ/4:95ꢄ
Cu(pyr)4(OTf)2(1 mol%)
ꢄ
PhI=NTs (1.0 eq)
Nucleophile (5.0 eq)
(NH4)2S2O8 (50 mol%)
MS4Å[a]
Nu
ꢄ
Ph
1a
NHTs
14a-21a
ꢅ(*&ꢀ
Solvent (0.5 M)
50 °C, Time
Ph
MeCN (0.5 M)
rt, 24 h;
ꢀꢁꢂꢃꢄꢅ ꢇꢀꢕ*ꢆꢈꢋ+ꢅ%ꢋ ꢌꢄ'ꢋ$ꢄꢅ+ꢋ#ꢋꢇꢋꢌꢂ$ꢄ
ꢀ
PhI=NTs (1.5 eq)
Cu(pyr)4(OTf)2
(5 mol%)
ꢆ(&)%ꢀ
ꢇ! #!ꢀ
XR
RX
ꢁ+0.3ꢀ ꢂ1$)&,-'()&ꢀ
ꢃ,)2&+0ꢀ
ꢊꢋꢌꢀ
ꢂ1ꢀꢄꢀ
(NH4)2S2O8
(50 mol%)
'!ꢀ
X
n
n
Ph
MS4Å[a]
MeCN (0.1 M)
rt, 24 h;
n NTs
50 °C, 2 h
ꢈꢀ
ꢐꢀ
ꢂ"ꢉꢂꢀ
4ꢉꢂꢀꢀꢈꢆꢁꢀ
ꢈꢍꢎꢀ
ꢏꢎꢀ
NHTs
Ph
Ph
26-29
22-25
30-33
ꢀ
ꢅ
3
ꢈ ꢁꢀꢑ"0ꢀꢉꢐꢓꢅꢅ
ꢈ ꢁꢉꢀꢑ"0ꢀꢉ ꢓꢀ
ꢈ ꢁꢕꢀꢏ ꢀ
ꢈ ꢁꢉꢕꢐꢏꢀ
-3..,)&ꢀ
ꢑꢉꢒꢐꢉ)ꢓꢐꢀ
ꢑꢉꢒꢐꢉ)ꢓꢐꢀ
2
ꢈꢔꢀ
ꢆ(&)%ꢀ
ꢇ! #!ꢀ
N
H
ꢁ+0.3ꢀ
ꢈꢀ
ꢃ1#/0."0&ꢀ
ꢝ.,%1$0ꢀ
ꢀ
ꢀ
ꢎꢎꢀ
ꢎꢐꢀ
ꢎꢆꢀ
O
ꢐꢏꢀ
ꢐꢈꢀ
ꢐꢎꢀ
ꢔꢙꢀ
ꢏꢎꢀ
ꢖꢙꢀ
ꢈꢊꢁꢅ
ꢀ
(+%,)&ꢀ
ꢖꢍꢎꢀ
ꢐ ꢀ
ꢖꢔꢀ
OH
NHTs
Ph
ꢀ
Ph
ꢀ
N
ꢅ
H
O
ꢙ ꢀ
ꢑꢐꢍ ꢕꢈꢓꢀ
ꢗꢀ
ꢂ"ꢘꢒ ꢉꢂꢀ
ꢂ"ꢂ ꢀ
ꢅꢒꢌꢀ
ꢊꢋꢌꢀ
4ꢒꢀꢀꢈꢋꢁꢀ
4ꢂ ꢀꢀꢈꢌꢁꢀ
OTBS
ꢐꢀ
ꢀ
Ph
O
O
ꢀ
NHTs
Ph
ꢀ
ꢖꢀ
ꢔꢀ
ꢈꢍꢎꢀ
ꢐꢍꢎꢀ
ꢚ ꢀ
ꢔꢔꢀ
O
O
ꢒꢛꢂꢒꢐ5ꢒꢉ)ꢀ ꢑꢉꢒꢐꢉ)ꢓꢐꢀ
4ꢂꢒꢛꢒꢀꢀꢈꢍꢁꢀ
4ꢘ.ꢀꢀꢎꢏꢁꢀ
O
Ph
OTBS
ꢀ
NHTs
Ph
ꢀ
ꢏꢗꢀ
ꢑꢔꢍꢏꢕꢈꢓꢀ
ꢏꢀ
ꢙꢀ
ꢜ(ꢘ.ꢀ
ꢊꢋꢌꢀ
ꢈꢔꢀ
ꢈꢗꢀ
O
OTBS
Ph
ꢗꢀ
ꢎ ꢀ
ꢐꢐꢀ
ꢏꢎꢀ
MeON
Ph
N
NHTs
ꢝꢋꢝꢃꢒꢀ
ꢑꢉꢒꢐꢉ)ꢓꢐꢀ
4ꢃꢝꢋꢝꢀꢀꢎꢈꢁꢀ
ꢖꢈꢀ
OMe
ꢀ
ꢀ
ꢀ "!ꢀ988ꢄꢃꢉ09/8ꢄꢃꢃ ꢈꢄ ꢎꢄ%ꢁꢂꢄ$%ꢅ#%ꢋꢌꢉꢄꢃꢅ%ꢂ#ꢋꢅꢈ$ꢄ(ꢂ#ꢂꢄ&$ꢂꢇ/ꢀ #!ꢀꢛ$ ꢈꢅ%ꢂꢇꢄ*ꢋꢂꢈꢇꢄ
ꢀ "!ꢀ988ꢄꢃꢉ09/8ꢄꢃꢃ ꢈꢄ ꢎꢄ%ꢁꢂꢄ$%ꢅ#%ꢋꢌꢉꢄꢃꢅ%ꢂ#ꢋꢅꢈ$ꢄ(ꢂ#ꢂꢄ&$ꢂꢇ/ꢀ #!ꢀꢛ$ ꢈꢅ%ꢂꢇꢄ*ꢋꢂꢈꢇ-ꢄ%ꢁꢂꢄ
!# ! #%ꢋ ꢌꢄ ꢎꢄ#ꢂꢉꢋ ꢋ$ ꢃꢂ#$ꢄꢉꢋ'ꢂꢌꢄꢋꢌꢄ!ꢅ#ꢂꢌ%ꢁꢂ$ꢂ$ꢄ(ꢅ$ꢄꢇꢂ%ꢂ#ꢃꢋꢌꢂꢇꢄꢊ*ꢄ9ꢒꢄꢓꢐꢝꢄ
$!ꢂꢆ%# $ꢆ !*/ꢄ
ꢀꢋꢌꢅꢈꢈ*,ꢄ(ꢂꢄꢋꢌ%ꢂꢉ#ꢅ%ꢂꢇꢄꢅꢌ %ꢁꢂ#ꢄꢕ&1ꢃꢂꢇꢋꢅ%ꢂꢇꢄꢆꢅ%ꢅꢈ*%ꢋꢆꢄꢆ*ꢆꢈꢂꢄ
% ꢄ %ꢁꢂꢄ ꢂ$%ꢅꢊꢈꢋ$ꢁꢂꢇꢄ ꢕ&1ꢅ$$ꢋ$%ꢂꢇꢄ %ꢅꢌꢇꢂꢃꢄ ꢆꢅ%ꢅꢈ*$ꢋ$ꢄ ꢅꢌꢇꢄ
ꢇꢂꢃ ꢌ$%#ꢅ%ꢂꢇꢄꢋ%$ꢄ$*ꢌ%ꢁꢂ%ꢋꢆꢄ&%ꢋꢈꢋ%*ꢄꢋꢌꢄ%ꢁꢂꢄꢂꢎꢎꢋꢆꢋꢂꢌ%ꢄ$*ꢌ%ꢁꢂ$ꢋ$ꢄ ꢎꢄ
ꢁꢋꢉꢁꢈ*ꢄ ꢂꢈꢅꢊ #ꢅ%ꢂꢄ ꢆ ꢃ! &ꢌꢇ$ꢄ ꢋꢌꢄ ꢅꢄ $%ꢂ!1ꢂꢆ ꢌ ꢃꢋꢆꢅꢈꢄ ꢃꢅꢌꢌꢂ#/ꢄ
ꢖꢂꢄꢂꢌ'ꢋ$ꢋ ꢌꢂꢇꢄ%ꢁꢅ%ꢄꢅꢄꢕ&1ꢆꢅ%ꢅꢈ*+ꢂꢇꢄꢋꢌꢇ ꢈꢋꢌꢂꢄꢎ #ꢃꢅ%ꢋ ꢌꢄ ꢎꢄ%ꢁꢂꢄ
:1!ꢁꢂꢌꢂ%*ꢈꢅꢃꢋꢌꢂꢄ ꢇꢂ#ꢋ'ꢅ%ꢋ'ꢂ$ꢄ ( &ꢈꢇꢄ ꢆꢆ&#ꢄ ꢊ*ꢄ %ꢁꢂꢄ !#ꢋ #ꢄ
ꢅ%%ꢅꢆꢁꢃꢂꢌ%ꢄ ꢎꢄ ꢅꢄ ꢁꢅꢈ ꢉꢂꢌꢄ ꢅ% ꢃꢄ ꢅ%ꢄ %ꢁꢂꢄ #%ꢁ 1! $ꢋ%ꢋ ꢌꢄ ꢎꢄ%ꢁꢂꢄ
$%*#ꢂꢌꢂꢄ $&ꢊ$%#ꢅ%ꢂ$ꢄ % ꢄ !# ꢇ&ꢆꢂꢄ ;1ꢎ&ꢌꢆ%ꢋ ꢌꢅꢈꢋ+ꢂꢇꢄ ꢋꢌꢇ ꢈꢋꢌꢂꢄ
ꢇꢂ#ꢋ'ꢅ%ꢋ'ꢂ$ꢄ2ꢘꢆꢁꢂꢃꢂꢄ;3/ꢄ
ꢄ
ꢍ ꢄ ꢂ)!ꢅꢌꢇꢄ %ꢁꢂꢄ $ꢆ !ꢂꢄ ꢎꢄ %ꢁꢂꢄ ꢌ&ꢆꢈꢂ !ꢁꢋꢈꢂ$,ꢄ (ꢂꢄ ꢂ)%ꢂꢌ$ꢋ'ꢂꢈ*ꢄ
ꢂ)ꢅꢃꢋꢌꢂꢇꢄ %ꢁꢂ#ꢄ ꢌ&ꢆꢈꢂ !ꢁꢋꢈꢂ$ꢄ 2ꢍꢅꢊꢈꢂꢄ <3/ꢄ ꢍꢁꢂꢄ ꢆ*ꢅꢌꢋꢇꢂꢄ ꢋ ꢌꢄ
#ꢂꢅꢆ%ꢂꢇꢄ $ꢃ %ꢁꢈ*ꢄ (ꢋ%ꢁꢄ %ꢁꢂꢄ ꢅ+ꢋ#ꢋꢇꢋꢌꢂꢄ ꢋꢌ%ꢂ#ꢃꢂꢇꢋꢅ%ꢂꢄ &! ꢌꢄ %ꢁꢂꢄ
ꢅꢇꢇꢋ%ꢋ ꢌꢄ ꢎꢄꢏꢐꢀꢄꢅ$ꢄꢅꢄꢆ 1$ ꢈ'ꢂꢌ%ꢄꢋꢌꢄ%ꢁꢂꢄ#ꢋꢌꢉ1 !ꢂꢌꢋꢌꢉꢄ!# ꢆꢂ$$ꢄ
% ꢄꢉꢋ'ꢂꢄꢅꢄꢉ ꢇꢄ*ꢋꢂꢈꢇꢄ ꢎꢄꢀꢄꢂꢄ2ꢂꢌ%#*ꢄ93/ꢄꢑꢆꢋꢇ1ꢈꢅꢊꢋꢈꢂꢄꢅꢌꢇꢄ )ꢋꢇꢅꢌ%1ꢄ
$ꢂꢌ$ꢋ%ꢋ'ꢂꢄ ꢁꢂ%ꢂ# ꢆ*ꢆꢈꢂ$ꢄ $&ꢆꢁꢄ ꢅ$ꢄ !*## ꢈꢂꢄ ꢅꢌꢇꢄ ꢋꢌꢇ ꢈꢂꢄ (ꢂ#ꢂꢄ
ꢋꢌ%# ꢇ&ꢆꢂꢇꢄ% ꢄ ꢊ%ꢅꢋꢌꢄ%ꢁꢂꢄꢆ ##ꢂ$! ꢌꢇꢋꢌꢉꢄ!# ꢇ&ꢆ%$ꢄꢋꢌꢄ ꢃ ꢇꢂ$%ꢄ
*ꢋꢂꢈꢇ$ꢄ 2ꢂꢌ%#ꢋꢂ$ꢄ :ꢄ ꢅꢌꢇꢄ ;3/ꢄ ꢒ*ꢇ#ꢋꢇꢂꢄ (ꢅ$ꢄ ꢋꢌ%# ꢇ&ꢆꢂꢇꢄ ꢊ*ꢄ &$ꢋꢌꢉꢄ
ꢓꢅꢔꢒ;ꢕꢓꢄ % ꢄ !# ꢇ&ꢆꢂꢄ ꢅꢄ ꢃꢋ)%&#ꢂꢄ ꢎꢄ :1ꢅꢌꢇꢄ 91!ꢁꢂꢌꢂ%*ꢈꢅꢃꢋꢌꢂꢄ
ꢇꢂ#ꢋ'ꢅ%ꢋ'ꢂ$ꢄ 2:/;.9/83ꢄ (ꢋ%ꢁꢄ @;Dꢄ *ꢋꢂꢈꢇꢄ 2ꢂꢌ%#*ꢄ <3/ꢄ ꢍꢁꢂꢄ #ꢂꢅꢆ%ꢋ ꢌꢄ
&$ꢋꢌꢉꢄ%ꢁꢂꢄꢌꢋ%# ꢉꢂꢌꢄꢌ&ꢆꢈꢂ !ꢁꢋꢈꢂ$ꢄꢅ+ꢋꢇꢂꢄꢋ ꢌ$ꢄꢅꢌꢇꢄꢁ*ꢇ# )*ꢈꢅꢃꢋꢌꢂꢄ
!# 'ꢋꢇꢂꢇꢄ %ꢁꢂꢄ 9,:1ꢇꢋꢅꢃꢋꢌꢂꢄ !#ꢂꢆ&#$ #$ꢅ ꢀꢆꢂꢄ ꢅꢌꢇꢄ ꢀꢇꢂ,ꢄ
#ꢂ$!ꢂꢆ%ꢋ'ꢂꢈ*ꢄ 2ꢂꢌ%#ꢋꢂ$ꢄ =ꢄ ꢅꢌꢇꢄ >3/49@5ꢄ ꢑꢄ ꢎ #ꢃꢅꢈꢄ ꢊ# ꢃ ꢅꢃꢋꢌꢅ%ꢋ ꢌꢄ
!# ꢆꢂꢂꢇꢂꢇꢄ (ꢋ%ꢁꢄ ꢋꢔ#ꢄ % ꢄ !# ꢇ&ꢆꢂꢄ ꢁꢈꢂ,ꢄ (ꢁꢋꢆꢁꢄ (ꢅ$ꢄ ꢅ$$ ꢆꢋꢅ%ꢂꢇꢄ
(ꢋ%ꢁꢄ%ꢁꢂꢄ#ꢂꢉꢋ ꢋ$ ꢃꢂ#ꢄꢅ$ꢄ%ꢁꢂꢄꢃꢋꢌ #ꢄ!# ꢇ&ꢆ%ꢄ2ꢂꢌ%#*ꢄ?3/ꢄꢀꢋꢌꢅꢈꢈ*,ꢄ
<1ꢃꢂ%ꢁ )*%ꢁꢋ !ꢁꢂꢌ ꢈꢄ (ꢅ$ꢄ ꢋꢌ%# ꢇ&ꢆꢂꢇꢄ % ꢄ ꢊ%ꢅꢋꢌꢄ %ꢁꢂꢄ ꢇꢂ$ꢋ#ꢂꢇꢄ
!# ꢇ&ꢆ%ꢄꢁꢀꢂꢄꢋꢌꢄꢅꢄꢃ ꢇꢂ#ꢅ%ꢂꢄ*ꢋꢂꢈꢇꢄ2ꢂꢌ%#*ꢄ@3/ꢄ
ꢄ
ꢊꢋꢌꢍ ꢍꢅꢃꢎꢄꢙꢌꢂ1ꢚ %ꢄꢛꢌꢇ ꢈꢋꢌꢂꢄꢘ*ꢌ%ꢁꢂ$ꢋ$ꢄ'ꢋꢅꢄꢘꢂ"&ꢂꢌ%ꢋꢅꢈꢄꢍ#ꢋ!ꢈꢂꢄꢕ&1ꢕꢅ%ꢅꢈ*$ꢋ$
ꢀ
Nu
Nu
Nu
Cu
Cu
Cu
X
NHP
N
Assisted-
tandem catalysis
X
P
ꢀ
ꢄ
ꢖꢋ%ꢁꢄ %ꢁꢋ$ꢄ ꢋꢇꢂꢅ,ꢄ (ꢂꢄ $&ꢊꢜꢂꢆ%ꢂꢇꢄ ꢁ1ꢊ# ꢃ $%*#ꢂꢌꢂꢄ ꢀꢍꢄ % ꢄ %ꢁꢂꢄ
ꢂ$%ꢅꢊꢈꢋ$ꢁꢂꢇꢄꢅ$$ꢋ$%ꢂꢇꢄ%ꢅꢌꢇꢂꢃꢄꢆꢅ%ꢅꢈ*%ꢋꢆꢄ!# ꢆꢂ$$/ꢄꢍꢁꢂꢌ, ꢆꢂ$ꢋ&ꢃꢄ
ꢀ
ꢆꢅ#ꢊ ꢌꢅ%ꢂꢄ ꢅꢌꢇꢄ % ꢈ&ꢂꢌꢂꢄ (ꢂ#ꢂꢄ ꢅꢇꢇꢂꢇꢄ% ꢄ%ꢁꢂꢄ #ꢂꢅꢆ%ꢋ ꢌꢄ ꢃꢋ)%&#ꢂꢄ
ꢊꢅ$ꢂꢇꢄ ꢌꢄ &#ꢄ ꢕ&1ꢆꢅ%ꢅꢈ*+ꢂꢇꢄ ꢅꢃꢋꢌꢅ%ꢋ ꢌꢄ #ꢂꢅꢆ%ꢋ ꢌ/4::5ꢄ ꢑ$ꢄ (ꢂꢄ
ꢂ)!ꢂꢆ%ꢂꢇ,ꢄ;1ꢃꢂ%ꢁ )*ꢄꢋꢌꢇ ꢈꢋꢌꢂꢄꢃꢄꢂꢅ(ꢅ$ꢄ ꢊ%ꢅꢋꢌꢂꢇꢄꢋꢌꢄ@=Dꢄ*ꢋꢂꢈꢇꢄ
ꢎ# ꢃꢄ ꢁ1ꢊ# ꢃ $%*#ꢂꢌꢂꢄ ꢀꢍꢄ 2ꢘꢆꢁꢂꢃꢂꢄ <3/4:;5ꢄ ꢍ ꢄ ꢂ)!ꢅꢌꢇꢄ %ꢁꢂꢄ
$&ꢊ$%#ꢅ%ꢂꢄ $ꢆ !ꢂ,ꢄ (ꢂꢄ %ꢁꢂꢌꢄ ꢆ ꢌꢇ&ꢆ%ꢂꢇꢄ ꢌꢂ1! %ꢄ ꢋꢌꢇ ꢈꢋꢌꢂꢄ
$*ꢌ%ꢁꢂ$ꢋ$ꢄ (ꢋ%ꢁꢄ 9,:1ꢇꢋ$&ꢊ$%ꢋ%&%ꢂꢇꢄ ꢈꢂꢎꢋꢌꢄ ꢀꢏ/ꢄ ꢑ$ꢄ ꢅꢄ #ꢂ$&ꢈ%,ꢄ %ꢁꢂꢄ
ꢇꢂ$ꢋ#ꢂꢇꢄ:,;1ꢇꢋ$&ꢊ$%ꢋ%&%ꢂꢇꢄꢋꢌꢇ ꢈꢋꢌꢂꢄꢃꢄꢐꢄꢆ &ꢈꢇꢄꢊꢂꢄ ꢊ%ꢅꢋꢌꢂꢇꢄꢅ$ꢄꢅꢄ
ꢃꢋ)%&#ꢂꢄ ꢎꢄ ꢇꢋꢅ$%ꢂ#ꢂ ꢃꢂ#$/ꢄ ꢀ&#%ꢁꢂ#ꢃ #ꢂ,ꢄ %ꢁꢋ$ꢄ ꢃꢂ%ꢁ ꢇꢄ ꢆ &ꢈꢇꢄ
ꢊꢂꢄꢅ!!ꢈꢋꢂꢇꢄ% ꢄꢅꢄ$%*#ꢂꢌꢂꢄ! $$ꢂ$$ꢋꢌꢉꢄ$&ꢊ$%ꢋ%&%ꢂꢇꢄꢅ# ꢃꢅ%ꢋꢆꢄ#ꢋꢌꢉꢄ
ꢖꢂꢄ %ꢁꢂꢌꢄ ꢂ)ꢅꢃꢋꢌꢂꢇꢄ %ꢁꢂꢄ %ꢅꢌꢇꢂꢃꢄ ꢆꢅ%ꢅꢈ*%ꢋꢆꢄ #ꢂꢅꢆ%ꢋ ꢌꢄ &$ꢋꢌꢉꢄ ꢅꢄ
$%*#ꢂꢌꢂꢄ ꢇꢂ#ꢋ'ꢅ%ꢋ'ꢂꢄ ꢊꢂꢅ#ꢋꢌꢉꢄ ꢅꢄ ꢌ&ꢆꢈꢂ !ꢁꢋꢈꢋꢆꢄ $ꢋ%ꢂꢄ ꢌꢄ %ꢁꢂꢄ $ꢋꢇꢂꢄ
ꢆꢁꢅꢋꢌ,ꢄ ꢂ)!ꢂꢆ%ꢋꢌꢉꢄ %ꢁꢅ%ꢄ ꢆ*ꢆꢈꢋ+ꢅ%ꢋ ꢌꢄ (ꢋꢈꢈꢄ ꢆꢆ&#ꢄ 'ꢋꢅꢄ %ꢁꢂꢄ
ꢋꢌ%#ꢅꢃ ꢈꢂꢆ&ꢈꢅ#ꢄꢅ%%ꢅꢆꢗꢄ ꢎꢄ%ꢁꢂꢄꢌ&ꢆꢈꢂ !ꢁꢋꢈꢋꢆꢄ$ꢋ%ꢂꢄ ꢌꢄ%ꢁꢂꢄꢅ+ꢋ#ꢋꢇꢋꢌꢂꢄ
#ꢋꢌꢉꢄ2ꢍꢅꢊꢈꢂꢄ=3/49A5ꢄꢑ$ꢄꢂ)!ꢂꢆ%ꢂꢇ,ꢄ%ꢁꢂꢄ$&ꢊ$%#ꢅ%ꢂꢄ(ꢋ%ꢁꢄ%ꢁꢂꢄ!#ꢋꢃꢅ#*ꢄ
ꢁ*ꢇ# )*ꢈꢄꢉ# &!ꢄꢁꢁꢄꢅꢎꢎ #ꢇꢂꢇꢄꢅꢄꢆ*ꢆꢈꢋꢆꢄꢂ%ꢁꢂ#ꢄ!# ꢇ&ꢆ%ꢄꢃꢈꢄ2ꢂꢌ%#*ꢄ93/ꢄ
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201900088
European Journal of Organic Chemistry
COMMUNICATION
ꢀꢁꢀ 0)ꢀ 1.(#/"ꢀ #(ꢁ)&#(ꢂꢀ ꢂꢃꢄꢀ #(ꢀ !))ꢁꢀ 5#ꢂ&ꢁ<ꢀ ꢃ(ꢀ /ꢄ),ꢂꢀ ) ꢀ
(1ꢄ&ꢂ),"#&ꢂ/9ꢀ >'ꢂ0"5&,5..)&ꢂꢀꢄ)1&ꢁꢀꢅꢂꢀ1/ꢂꢁꢀ ).ꢀ0"#/ꢀ.ꢂꢆꢄ0#)(ꢀ
0)ꢀ ).'ꢀ #(ꢁ)&#(ꢂꢀ ꢂꢃꢅꢆ "ꢆ2#(!ꢀ "ꢂ0ꢂ.)ꢄ5ꢄ&#ꢄꢀ .#(!ꢀ ꢆ0ꢀ 0"ꢂꢀ ꢇ>Iꢀ
,)/#0#)(<ꢀ ꢈ#(ꢆ&&59ꢀ 0"ꢂꢀ .ꢂꢆꢄ0#)(ꢀ ) ꢀ J>ꢄ"&).)0"#),"ꢂ()&ꢀ ꢆ/ꢀ ꢆꢀ
(1ꢄ&ꢂ),"#&ꢂꢀ!ꢆ2ꢂꢀ#(ꢁ)&#(ꢂꢀꢂꢃꢇꢀ#(ꢀꢆꢀ')ꢁꢂ/0ꢀ5#ꢂ&ꢁ<ꢀ
ꢀꢀꢀꢀꢈ1.0"ꢂ.').ꢂ9ꢀꢆꢀ/05.ꢂ(ꢂꢀꢁꢂ.#2ꢆ0#2ꢂꢀꢅꢂꢆ.#(!ꢀ ꢆꢀ/#&5&)45,.),5&ꢀ
ꢄ"ꢆ#(ꢀꢂꢈꢀ1(ꢁꢂ.3ꢂ(0ꢀ0"ꢂꢀ#(0ꢂ!.ꢆ0ꢂꢁꢀ0".ꢂꢂꢀ/ꢂ-1ꢂ(0#ꢆ&ꢀꢄꢆ0ꢆ&50#ꢄꢀ
ꢄ5ꢄ&ꢂ/ꢀ0)ꢀ,.)2#ꢁꢂꢀI9I>/,#.)ꢄ5ꢄ&#ꢄꢀ#(ꢁ)&#(ꢂꢀꢂꢉꢀ@ꢉꢄ"ꢂ'ꢂꢀKA<ꢀ
ꢀ
ꢉꢃꢊꢂꢁꢋꢄ ꢌꢍ ꢎ ꢂꢏꢆꢈ
ꢌ"#/ꢀ 3).%ꢀ 3ꢆ/ꢀ /1,,).0ꢂꢁꢀ ꢅ5ꢀ ꢐꢉꢑꢉꢀ ꢒꢊꢒꢓꢍ ꢃꢀ ꢔ.ꢆ(0ꢀ ꢍ1'ꢅꢂ./ꢀ
ꢐꢑGN FJHIGꢀ #(ꢀ ꢑ.ꢂꢄ#/ꢂ&5ꢀ ꢕꢂ/#!(ꢂꢁꢀ ꢇꢆ0ꢆ&5/0/ꢀ 3#0"ꢀ ꢇ1/0)'#6ꢂꢁꢀ
ꢉꢄꢆ )&ꢁ#(!ꢀꢆ(ꢁꢀꢐꢑGN FJLJHꢀ#(ꢀ 5ꢅ.#ꢁꢀꢇꢆ0ꢆ&5/#/9ꢀꢆꢀꢔ.ꢆ(0>#(ꢀꢆ#ꢁꢀ ).ꢀ
ꢉꢄ#ꢂ(0# #ꢄꢀꢏꢂ/ꢂꢆ.ꢄ"ꢀ@ꢖAꢀ@GN FHKJOAꢀꢆ(ꢁꢀ@ꢇAꢀ@GMꢒFNHFJA<ꢀ
ꢀꢁꢂꢐꢄꢇꢃꢏꢈꢁꢐꢈꢇꢂꢏ ꢑ ꢆꢏꢈ
ꢊꢄꢋꢇꢁꢇꢆꢃꢌꢀꢊ,,&#ꢄꢆ0#)(ꢀ0)ꢀ'1&0#>/1ꢅ/0#010ꢂꢁꢀ#(ꢁ)&#(ꢂꢀ/5(0"ꢂ/#/ꢀ
PhI=NTs
(1.0 eq)
Cu(pyr)4(OTf)2 (NH4)2S2O8
(5 mol%)
ꢌ"ꢂꢀꢆ10")./ꢀꢁꢂꢄ&ꢆ.ꢂꢀ()ꢀꢄ)( &#ꢄ0ꢀ) ꢀ#(0ꢂ.ꢂ/0<ꢀ
nucleophile
Cs2CO3
(3.0 eq)
Nu
R2
(50 mol%)
solvent
R1
R2
R3
R3
ꢒ ꢓꢋꢁꢑꢌꢆꢔꢀꢁꢂꢃꢄꢅꢆꢀꢇꢂꢁꢂꢈꢉꢊꢋꢊꢀꢌꢀꢍꢎꢏꢇꢂꢁꢂꢈꢉꢊꢋꢊꢀꢌꢀꢄꢐꢎꢑꢈꢅꢀ
R1
MS4Å, MeCN
rt, 24-48 h;
toluene
N
Br
Ts
34a-e
ꢎꢃꢇꢁꢋꢐꢃꢂꢈꢋꢒꢂꢁꢋꢐꢃꢀꢌꢀꢋꢃꢄꢐꢈꢋꢃꢅꢀꢌꢀꢊꢓꢋꢔꢐꢇꢉꢇꢈꢅꢀ
reflux, time; reflux, 2-24 h
1e, 1l, 1m
aziridination nucleophilic amination
ring opening
BGCꢀꢀ ꢈ).ꢀ.ꢂ2#ꢂ3/ꢀ) ꢀ0ꢆ(ꢁꢂ'ꢀꢄꢆ0ꢆ&5/#/9ꢀ/ꢂꢂ;ꢀꢆAꢀꢕ<ꢀꢓ<ꢀꢈ)!!9ꢀꢓ<ꢀꢍ<ꢀꢁ)/ꢀꢉꢆ(0)/9ꢀꢀꢁꢁꢂꢃ"ꢄ
ꢀꢅꢆꢇ"ꢄꢈꢆꢉ"9ꢀꢍꢎꢎꢃ9ꢀ%'+9ꢀHILK?HIMO:ꢀꢅAꢀꢐ<ꢀꢔ&ꢂꢆ/)(9ꢀꢊ<ꢀꢊ$ꢆ'ꢆ#(9ꢀꢊꢋꢌꢆ "ꢄꢀꢅꢆꢇ"ꢄ
ꢍꢋꢎ"ꢄꢄ ꢏꢃ"9ꢀꢍꢎꢎꢃ9ꢀ '&9ꢀIMKJ:ꢀ ꢄAꢀ ꢉ<ꢀꢇ"ꢆ(!9ꢀꢀꢅꢆꢇ"ꢄ ꢐꢁꢑ"ꢄꢈꢆꢉ"9ꢀꢍꢎꢎꢃ9ꢀ&&9ꢀ IFH<ꢀ ꢁAꢀ ꢏ<ꢀ
ꢖꢆ%ꢂ.9ꢀꢔ<ꢀꢖꢆ6ꢆ(9ꢀꢀꢅꢆꢇ"ꢄꢈꢆꢉ"9ꢄꢍꢎꢎꢈ9ꢀ$#(9ꢀGFFG<ꢀ
MeOH
(50 equiv)
24 h;
OMe
OMe
Me
OMe
MeOH
MeOH
(50 eq)
1 h;
MeO
MeO
(50 equiv)
1-2 h;
BHCꢀ ꢈ).ꢀ/ꢂ&ꢂꢄ0ꢂꢁꢀꢂ4ꢆ',&ꢂ/ꢀ) ꢀ).0")!)(ꢆ&ꢀ0ꢆ(ꢁꢂ'ꢀꢄꢆ0ꢆ&5/#/9ꢀ/ꢂꢂ;ꢀꢆAꢀꢍ<ꢀꢐꢂ)(!9ꢀꢉ<ꢀꢕ<ꢀ
ꢉꢂ)9ꢀꢐ<ꢀꢗ<ꢀꢐ<ꢀꢉ"#(9ꢀꢒ"ꢄꢊꢇ"ꢄꢀꢅꢆꢇ"ꢄꢐꢁꢑ"9ꢀꢍꢎꢎꢎ9ꢀ$%%9ꢀGFHHF:ꢀꢅAꢀꢗ<ꢀꢍ#/"#ꢅꢆ5ꢆ/"#9ꢀꢎ<ꢀ
ꢗ)/"#%ꢆ3ꢆ9ꢀ ꢗ<ꢀ ꢃ(ꢆꢁꢆ9ꢀ ꢎ<ꢀ ꢕ<ꢀ ꢎ#&0)(9ꢀ ꢎ<ꢀ #ꢁꢆ#9ꢀ ꢉ<ꢀ ꢘꢂ'1.ꢆ9ꢀꢊꢋꢌꢆ "ꢄ ꢀꢅꢆꢇ"ꢄ ꢍꢋꢎ"ꢄ
ꢏꢃ"9ꢀ ꢍꢎꢎꢂ9ꢀ '%9ꢀ HLNG:ꢀ ꢄAꢀ ꢎ<ꢀ ꢕ<ꢀ ꢎ#&0)(9ꢀ ꢗ<ꢀ ꢃ(ꢆꢁꢆ9ꢀ ꢗ<ꢀ ꢍ#/"#ꢅꢆ5ꢆ/"#9ꢀ ꢉ<ꢀ ꢘꢂ'1.ꢆ9ꢀ
ꢀꢅꢆꢇ"ꢄ ꢀꢁꢇꢇꢓꢋ"9ꢀꢍꢎꢎꢃ9ꢀ HMGH:ꢀ ꢁAꢀ ꢉ<ꢀ ꢈ.ꢆ(ꢄꢂ9ꢀ ꢎ<ꢀ <ꢀ ꢉ"ꢆ"9ꢀꢊ<ꢀ ꢙꢂꢆ0"ꢂ.3ꢆ49ꢀ <ꢀ
ꢙꢆꢄ%9ꢀꢐ<ꢀꢑ<ꢀꢏ)0"9ꢀꢌ<ꢀꢚꢂꢄ0%ꢆ9ꢀꢒ"ꢄꢊꢇ"ꢄꢀꢅꢆꢇ"ꢄꢐꢁꢑ"9ꢀꢍꢎꢎꢈ9ꢀ$%*9ꢀGHFL<ꢀꢈ).ꢀ/ꢂ&ꢂꢄ0ꢂꢁꢀ
ꢂ4ꢆ',&ꢂ/ꢀ ) ꢀ ꢆ10)>0ꢆ(ꢁꢂ'ꢀ ꢄꢆ0ꢆ&5/#/9ꢀ /ꢂꢂ;ꢀ ꢂAꢀ ꢉ<ꢀ ꢗꢆ'ꢆ/ꢆ%#9ꢀ ꢎ<ꢀ ꢒꢆ(ꢆ#9ꢀ ꢎ<ꢀ
ꢉ"#ꢅꢆ/ꢆ%#9ꢀꢒ"ꢄꢊꢇ"ꢄꢀꢅꢆꢇ"ꢄꢐꢁꢑ"9ꢀꢍꢎꢎꢀ9ꢀ$%&9ꢀGHKL:ꢀ Aꢀꢙ<ꢀꢉ<ꢀꢇ"ꢂ1(!9ꢀꢏ<ꢀꢐ<ꢀꢑꢆ0ꢄ"9ꢀꢎ<ꢀ
ꢏ<ꢀ ꢑ&ꢆ5ꢂ.9ꢀ ꢒ"ꢄ ꢔꢂꢌ"ꢄ ꢀꢅꢆꢇ"9ꢀ ꢍꢎꢎꢈ9ꢀ *#9ꢀ IMJG:ꢀ !Aꢀ <ꢀ ꢘꢂꢁꢆ9ꢀ ꢎ<ꢀ ꢗꢆ'ꢆ!1ꢄ"#9ꢀ <ꢀ
ꢒꢆ'ꢂ5ꢆ9ꢀꢒ<ꢀꢉ1!#')0)9ꢀꢀ <ꢀꢌ)%15ꢆ'ꢆ9ꢀꢔꢂꢌ"ꢄꢕꢆꢎꢎ"9ꢀꢍꢎꢀꢃ9ꢀ$)9ꢀJOJN<ꢀꢈ).ꢀ/ꢂ&ꢂꢄ0ꢂꢁꢀ
ꢂ4ꢆ',&ꢂ/ꢀ ) ꢀ ꢆ//#/0ꢂꢁꢀ 0ꢆ(ꢁꢂ'ꢀ ꢄꢆ0ꢆ&5/#/9ꢀ /ꢂꢂ;ꢀ "Aꢀ ꢒ<ꢀ ꢚ#9ꢀ ꢗ<ꢀ ꢛꢂ(!9ꢀ ꢖ<ꢀ
ꢍꢂ1ꢂ(/3ꢆ(ꢁꢂ.9ꢀꢐ<ꢀꢊ<ꢀꢌ1(!ꢂ9ꢀꢒ"ꢄꢔꢂꢌ"ꢄꢀꢅꢆꢇ"9ꢀꢍꢎꢎꢈ9ꢀ*#9ꢀLKGK:ꢀ#Aꢀ <ꢀꢕ19ꢀꢒ<ꢀꢕ#(!9ꢀ
ꢔꢂꢌ"ꢄꢕꢆꢎꢎ"9ꢄꢍꢎꢎꢂ9ꢀ(9ꢀGFOG:ꢀ$Aꢀꢐ<ꢀꢔ<ꢀꢒ#'9ꢀꢒ<ꢀꢎ<ꢀꢙꢆ&069ꢀꢃ<ꢀꢈ<ꢀꢔꢆ.ꢄ#ꢆ9ꢀꢕ<ꢀꢒ3#ꢆ0%)3/%#9ꢀ
ꢑ<ꢀ ꢐ<ꢀ ꢙꢆ&/"9ꢀ ꢒ"ꢄ ꢊꢇ"ꢄ ꢀꢅꢆꢇ"ꢄ ꢐꢁꢑ"9ꢀ ꢍꢎꢎꢃ9ꢀ $%)9ꢀ GHKNF:ꢀ %Aꢀ ꢑ<ꢀ ꢊ<ꢀ ꢓ2ꢆ(/9ꢀ ꢐ<ꢀ ꢓ<ꢀ
ꢏ)ꢅ#(/)(9ꢀꢒ"ꢄꢊꢇ"ꢄꢀꢅꢆꢇ"ꢄꢐꢁꢑ"9ꢀꢍꢎꢎꢀ9ꢀ$%&9ꢀJLFO:ꢀ&Aꢀꢊ<ꢀꢍ<ꢀꢌ"ꢆꢁꢆ(#9ꢀꢜ<ꢀ <ꢀꢏꢆ3ꢆ&9ꢀ
ꢔꢂꢌ"ꢄꢕꢆꢎꢎ"9ꢀꢍꢎꢎꢍ9ꢀ'9ꢀJIH:ꢀ 'Aꢀꢉ<ꢀꢘ<ꢀ ꢉ)(9ꢀꢒ<ꢀ <ꢀ ꢑꢆ.%9ꢀ ꢗ<ꢀꢒ<ꢀꢇ"1(!9ꢀ ꢒ"ꢄꢊꢇ"ꢄ ꢀꢅꢆꢇ"ꢄ
ꢐꢁꢑ"9ꢀꢍꢎꢎꢍ9ꢀ$%'9ꢀLNIN<ꢀ
65%
N
N
N
85%[a]
79%[a]
Ts
34a
Ts
Ts
(d.r. = 38:1)[a], [b], [c]
34b
34c
Cl
N-Methylpyrrole
(5.0 equiv)
NMe
4-ClC6H4SH
(5.0 equiv)
2 h;
56%[a]
S
(CH2Cl)2, 12 h;
53%
(r.r. =5:4)[a], [c]
N
N
Ts
Ts
34d
34e
ꢀ
ꢀBꢆCꢃ/)&ꢆ0ꢂꢁꢀ5#ꢂ&ꢁꢀBꢅCꢀꢇ1@,5.AJ@ꢋꢌ AHꢀ @GFꢀ ')&RAꢀ ꢆ(ꢁꢀ @ꢍ JAHꢉHꢋNꢀ@G<Fꢀꢂ-1#2Aꢀ3ꢂ.ꢂꢀ
1/ꢂꢁ<ꢀBꢄCꢀꢁ#ꢆ/0ꢂ.ꢂ)'ꢂ.#ꢄꢀ.ꢆ0#)ꢀꢆ(ꢁꢀ.ꢂ!#)#/)'ꢂ.#ꢄꢀ.ꢆ0#)ꢀ3ꢂ.ꢂꢀꢁꢂ0ꢂ.'#(ꢂꢁꢀꢅ5ꢀG
ꢀ
ꢍꢎꢏꢀ/,ꢂꢄ0.ꢆ<ꢀ
ꢆ
ꢊꢄꢋꢇꢁꢇꢆꢈꢌꢀꢊ,,&#ꢄꢆ0#)(ꢀ0)ꢀꢉ,#.)ꢀꢇ5ꢄ&#6ꢆ0#)(ꢀ
PhI=NTs (1.5 eq)
TMSO
Cu(MeCN)4PF6 (5 mol%)
MS4Å
3
(NH4)2S2O8 (50 mol%)
reflux, 2 h
BICꢀ ꢆAꢀꢑ<ꢀꢊ<ꢀꢙꢂ(ꢁꢂ.9ꢀꢎ<ꢀꢑ<ꢀꢇ.)ꢆ009ꢀꢖ<ꢀꢙ#01&/%#9ꢀꢖꢆꢎꢂꢗꢅꢆꢃꢂꢁꢋ9ꢀꢍꢎꢎꢏ9ꢀ)%9ꢀMKFK:ꢀꢅAꢀꢑ<ꢀ
ꢊ<ꢀꢙꢂ(ꢁꢂ.9ꢀꢜ<ꢀꢊ<ꢀꢜꢂ.'ꢆ9ꢀꢌ<ꢀꢐ<ꢀꢑꢆ40)(9ꢀꢌ<ꢀ <ꢀꢑ#&&)39ꢀꢊꢑꢑ"ꢄꢀꢅꢆꢇ"ꢄꢈꢆꢘ"9ꢀꢍꢎꢎꢐ9ꢀ'$9ꢀ
JF:ꢀ@ꢑAꢀꢑ<ꢀꢊ<ꢀꢙꢂ(ꢁꢂ.9ꢀ ꢗꢎ"ꢄꢙꢂꢁꢃ"ꢄꢈꢆꢚ"9ꢀꢍꢎꢀꢃ9ꢀ&$9ꢀJII<ꢀ
MeCN (0.25 M)
rt, 24 h;
Br
35
BJCꢀꢀꢀ ꢈ).ꢀ /ꢂ&ꢂꢄ0ꢂꢁꢀ ꢂ4ꢆ',&ꢂ/ꢀ ) ꢀ 'ꢂ0ꢆ0"ꢂ/#/="5ꢁ.)!ꢂ(ꢆ0#)(ꢀ ) ꢀ )&ꢂ #(/ꢀ /ꢂ-1ꢂ(ꢄꢂ9ꢀ
/ꢂꢂ;ꢀꢆAꢀꢉ<ꢀꢐ<ꢀꢎꢄꢚꢆ#(9ꢀꢓ<ꢀꢈ<ꢀꢎꢄꢇ).ꢁ9ꢀꢉ<ꢀꢕ<ꢀꢊ.0"1.9ꢀꢓ<ꢀ ꢆ1,0'ꢆ(9ꢀꢐ<ꢀꢈꢂ&ꢁ'ꢆ(9ꢀꢙ<ꢀ
ꢊ<ꢀꢍ1!ꢂ(09ꢀꢚ<ꢀꢒ<ꢀꢐ)"(/)(9ꢀꢉ<ꢀꢎꢂꢄ%#(!9ꢀꢎ<ꢀꢖ.))%"ꢆ.09ꢀꢙꢁꢛ!ꢇ"ꢄꢜꢗꢎꢆꢂ"ꢄꢐꢑꢝ"ꢄꢏꢋꢌ"9ꢀ
ꢀꢑꢑꢉ9ꢀ *)9ꢀ HJL:ꢀ ꢅAꢀ ꢑ<ꢀꢖ+./0#(!9ꢀ ꢑ<ꢀ ꢍ#ꢂ&/ꢂ(9ꢀ ꢀꢅꢆꢇ<ꢄ ꢀꢁꢇꢇꢓꢋ<9ꢄ ꢍꢎꢎꢍ9ꢀ HGJF<ꢀ ꢈ).ꢀ
/ꢂ&ꢂꢄ0ꢂꢁꢀꢂ4ꢆ',&ꢂ/ꢀ) ꢀ'ꢂ0ꢆ0"ꢂ/#/=#/)'ꢂ.#6ꢆ0#)(ꢀ/ꢂ-1ꢂ(ꢄꢂ9ꢀ/ꢂꢂ;ꢀꢄAꢀꢜ<ꢀꢖ*"./ꢄ"9ꢀ
ꢉ<ꢀ ꢖ&ꢂꢄ"ꢂ.09ꢀ ꢀꢅꢆꢇ"ꢄ ꢀꢁꢇꢇꢓꢋ"9ꢄ ꢍꢎꢎꢏ9ꢀ GOLN<ꢀ ꢈ).ꢀ /ꢂ&ꢂꢄ0ꢂꢁꢀ ꢂ4ꢆ',&ꢂ/ꢀ ) ꢀ
'ꢂ0ꢆ0"ꢂ/#/="5ꢁ.)!ꢂ(ꢆ0#)(ꢀ ) ꢀ %ꢂ0)(ꢂ/ꢀ ).ꢀ ꢁꢂ"5ꢁ.)!ꢂ(ꢆ0#)(ꢀ ) ꢀ ꢆ&ꢄ)")&/ꢀ
/ꢂ-1ꢂ(ꢄꢂ9ꢀ/ꢂꢂ;ꢀꢁAꢀꢐ<ꢀꢚ)1#ꢂ9ꢀꢇ<ꢀꢙ<ꢀꢖ#ꢂ&ꢆ3/%#9ꢀꢏ<ꢀ <ꢀꢔ.1ꢅꢅ/9ꢄꢒ"ꢄꢊꢇ"ꢄꢀꢅꢆꢇ"ꢄꢐꢁꢑ"9ꢄ
ꢍꢎꢎꢀ9ꢀ $%&9ꢀ GGIGH<ꢀ ꢈ).ꢀ ꢆꢀ /ꢂ&ꢂꢄ0ꢂꢁꢀ ꢂ4ꢆ',&ꢂꢀ ) ꢀ 'ꢂ0ꢆ0"ꢂ/#/=)4#ꢁꢆ0#)(ꢀ 3#0"ꢀ
,ꢂ.)4#ꢁꢂ/ꢀ/ꢂ-1ꢂ(ꢄꢂ9ꢀ/ꢂꢂ;ꢀꢂAꢀꢉ<ꢀꢖꢂ&#!(59ꢀꢉ<ꢀꢓ&#ꢅꢆ1ꢂ.9ꢀꢉ<ꢀꢎꢆꢂꢄ"&#(!9ꢀꢉ<ꢀꢖ&ꢂꢄ"ꢂ.09ꢀ
ꢊꢋꢌꢆ "ꢄ ꢀꢅꢆꢇ"ꢄ ꢍꢋꢎ"ꢄ ꢏꢃ"9ꢀ ꢍꢎꢎꢏ9ꢀ '(9ꢀ GOFF:ꢀ Aꢀ ꢖ<ꢀ ꢉꢄ"'#ꢁ09ꢀ ꢉ<ꢀ ꢒ.ꢂ"&9ꢀ ꢀꢅꢆꢇ"ꢄ
ꢀꢁꢇꢇꢓꢋ"9ꢄꢍꢎꢀꢀ9ꢀ'*9ꢀKNMO<ꢀ
BKCꢀ ꢊ<ꢀꢖꢂ5ꢂ.9ꢀꢌ<ꢀꢇꢆ/0ꢆ("ꢂ#.)9ꢀꢑ<ꢀꢖ1/ꢄꢆ9ꢀꢔ<ꢀꢑ.ꢂ/0ꢆ09ꢀꢀꢅꢆꢇꢀꢗꢎꢀꢅꢆꢇ9ꢄꢍꢎꢀꢈ9ꢀ*9ꢀHJII<ꢀ
BLCꢀ ꢈ).ꢀ ꢂ4ꢆ',&ꢂ/ꢀ ) ꢀ ꢆꢀ /ꢂ-1ꢂ(0#ꢆ&ꢀꢆ&%ꢂ(ꢂꢀꢆ6#.#ꢁ#(ꢆ0#)(=(1ꢄ&ꢂ),"#&#ꢄꢀ .#(!ꢀ ),ꢂ(#(!ꢀ
3#0"ꢀꢏ">ꢄꢆ0ꢆ&5/0/9ꢀ/ꢂꢂ;ꢀꢆAꢀꢓ<ꢀꢚꢂ2#0ꢂ/>ꢊ!ꢆꢅꢆꢅꢆ9ꢀꢓ<ꢀꢎꢂ("ꢆ$#9ꢀꢚ<ꢀꢍ<ꢀꢑꢂ.&/)(9ꢀꢇ<ꢀꢎ<ꢀ
ꢏ)$ꢆ/9ꢀꢔꢂꢌ"ꢄꢕꢆꢎꢎ"9ꢀꢍꢎꢎꢍ9ꢀ'9ꢀNLI:ꢀꢅAꢀꢏ<ꢀꢖ)ꢁ(ꢂ.9ꢀꢖ<ꢀꢒ<ꢀꢎꢆ.ꢄꢂ&&#()9ꢀꢊ<ꢀꢉꢂ2ꢂ.#()9ꢀꢊ<ꢀ
ꢚ<ꢀ ꢉ'ꢂ(0)(9ꢀ ꢇ<ꢀ ꢎ<ꢀ ꢏ)$ꢆ/9ꢀ ꢒ"ꢄ ꢔꢂꢌ"ꢄ ꢀꢅꢆꢇ"9ꢀ ꢍꢎꢎꢈ9ꢀ *#9ꢀ IONN:ꢀ ꢄAꢀ ꢏ<ꢀ ꢔ1,0ꢆ9ꢀ ꢒ<ꢀ ꢎ<ꢀ
ꢉ)!#9ꢀꢉ<ꢀꢓ<ꢀꢖꢂ.(ꢆ.ꢁ9ꢀꢐ<ꢀꢕ<ꢀꢕꢂꢄꢆ01.9ꢀꢇ<ꢀꢎ<ꢀꢏ)$ꢆ/9ꢀꢔꢂꢌ"ꢄꢕꢆꢎꢎ"9ꢀꢍꢎꢎꢑ9ꢀ$$9ꢀGKHM:ꢀꢁAꢀꢉ<ꢀ
ꢖ100ꢆ.9ꢀꢐ<ꢀꢇꢆ#(ꢂ9ꢀꢓ<ꢀꢔ)(ꢝ9ꢀꢏ<ꢀ ꢆ..#/9ꢀꢐ<ꢀꢔ#&&'ꢆ(9ꢀꢏ<ꢀꢊ0#ꢂ(6ꢆ9ꢀꢏ<ꢀꢔ1,0ꢆ9ꢀꢒ<ꢀꢎ<ꢀꢉ)!#9ꢀ
ꢚ<ꢀꢐꢆ#(9ꢀꢍ<ꢀꢇ<ꢀꢊꢅꢆ/ꢄꢆ&9ꢀꢗ<ꢀꢚꢂ2#(ꢂ9ꢀꢚ<ꢀꢎ<ꢀꢏꢂ,%ꢆ9ꢀꢇ<ꢀꢎ<ꢀꢏ)$ꢆ/9ꢀꢒ"ꢄꢔꢂꢌ"ꢄꢀꢅꢆꢇ"9ꢀꢍꢎꢀꢐ9ꢀ
+&9ꢀNFKJ:ꢀꢂAꢀꢊ<ꢀꢑꢆꢁ3ꢆ9ꢀꢌ<ꢀꢉ0ꢂ(!ꢂ&9ꢀꢔꢂꢌ"ꢄꢕꢆꢎꢎ"9ꢀꢍꢎꢎꢍ9ꢀ'9ꢀHGIM:ꢀ Aꢀꢊ<ꢀꢑꢆꢁ3ꢆ9ꢀꢊ<ꢀꢇ<ꢀ
ꢈ&#ꢄ%9ꢀꢇ<ꢀꢊ<ꢀꢚꢂ2ꢂ.ꢂ009ꢀꢌ<ꢀꢉ0ꢂ(!ꢂ&9ꢀꢒ"ꢄꢔꢂꢌ"ꢄꢀꢅꢆꢇ"9ꢀꢍꢎꢎꢃ9ꢀ),9ꢀLIMM:ꢀ!Aꢀꢔ<ꢀꢇ<ꢀꢈꢂꢆ/09ꢀꢚ<ꢀ
ꢙ<ꢀꢑꢆ!ꢂ9ꢀꢐ<ꢀꢏ)ꢅꢂ.0/)(9ꢀꢀꢅꢆꢇ"ꢄꢀꢁꢇꢇꢓꢋ"9ꢀꢍꢎꢀꢎ9ꢀ')9ꢀHNIK:ꢀ"Aꢀꢙ<ꢀꢑ<ꢀꢘ(/3).0"9ꢀ
ꢉ<ꢀ ꢔ<ꢀ ꢚꢆ')(09ꢀ ꢐ<ꢀ ꢏ)ꢅꢂ.0/)(9ꢀ ꢖꢆꢎꢂꢗꢅꢆꢃꢂꢁꢋ9ꢀ ꢍꢎꢀꢃ9ꢀ *#9ꢀ MINN:ꢀ #Aꢀ ꢍ<ꢀ ꢔ#!ꢆ(09ꢀ ꢔ<ꢀ
O
O
Cs2CO3 (3.0 eq)
toluene (0.25 M)
NHTs
N
reflux, 12 h
Br
36
Ts
37%
37
ꢀ
ꢀ
ꢀꢁꢂꢃꢄꢅꢆꢇꢁꢂꢆꢈꢈ
ꢈ
ꢀꢃ(ꢀ /1''ꢆ.59ꢀ 3ꢂꢀ ꢁꢂ2ꢂ&),ꢂꢁꢀ ꢆ(ꢀ ꢂ #ꢄ#ꢂ(0ꢀ ).'ꢆ&ꢀ ꢁ)1ꢅ&ꢂꢀ
1(ꢄ0#)(ꢆ&#6ꢆ0#)(ꢀ ,.)ꢄꢂ//ꢀ 0".)1!"ꢀ ꢇ1>'ꢂꢁ#ꢆ0ꢂꢁꢀ ꢆ//#/0ꢂꢁꢀ
0ꢆ(ꢁꢂ'ꢀ ꢄꢆ0ꢆ&5/#/<ꢀ @ꢍ JAHꢉHꢋNꢀ 3ꢆ/ꢀ ꢂ ꢂꢄ0#2ꢂꢀ ꢆ/ꢀ ꢆꢀ 0.#!!ꢂ.ꢀ
.ꢂꢆ!ꢂ(0ꢀ ).ꢀ0"ꢂꢀ#(ꢀ/#01ꢀꢄ)(2ꢂ./#)(ꢀ) ꢀ0"ꢂꢀꢇ1ꢀꢄꢆ0ꢆ&5/09ꢀꢆ(ꢁꢀ0"ꢂꢀ
(1ꢄ&ꢂ),"#&#ꢄꢀ .#(!ꢀ ),ꢂ(#(!ꢀ ) ꢀ ꢆ6#.#ꢁ#(ꢂꢀ 3ꢆ/ꢀ ꢂ ꢂꢄ0#2ꢂ&5ꢀ
ꢆꢄ#&#0ꢆ0ꢂꢁ<ꢀ ꢌ"ꢂꢀ ꢂ/0ꢆꢅ&#/"ꢂꢁꢀ ꢆ//#/0ꢂꢁꢀ 0ꢆ(ꢁꢂ'ꢀ ꢄꢆ0ꢆ&5/#/ꢀ 3ꢆ/ꢀ
1.0"ꢂ.ꢀ ꢂ4,ꢆ(ꢁꢂꢁꢀ 0)ꢀ 0"ꢂꢀ "#!"&5ꢀ#(0ꢂ!.ꢆ0ꢂꢁꢀ 0".ꢂꢂꢀ ꢄ)(0#!1)1/ꢀ
ꢄꢆ0ꢆ&50#ꢄꢀ/5/0ꢂ'9ꢀ3"#ꢄ"ꢀ3ꢆ/ꢀ,.)2ꢂꢁꢀ0)ꢀꢅꢂꢀ1/ꢂ 1&ꢀ ).ꢀ)ꢅ0ꢆ#(#(!ꢀ
1(ꢄ0#)(ꢆ&#6ꢂꢁꢀ#(ꢁ)&#(ꢂ/<
ꢆ
ꢈ
ꢈ
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201900088
European Journal of Organic Chemistry
COMMUNICATION
ꢀꢁ04$1ꢁ;>ꢂꢃAꢂꢄꢁ3ꢅ$))ꢁꢅ4>ꢂꢆAꢂꢇ$))ꢅ$;ꢁꢅ4>ꢂꢃAꢂꢀꢅ4ꢈꢅ+>ꢂꢀꢁꢂꢃꢄꢅꢆꢇꢈꢄꢅꢉꢄ>ꢂ ꢀꢁ >ꢂꢊ&>ꢂTK?ꢂ'Eꢂ
ꢇAꢂ ꢀꢁ04$1ꢁ;>ꢂ ꢉAꢂ ꢊ$ꢁ2$ꢁ)2($>ꢂ ꢃAꢂ ꢄꢁ3ꢅ$))ꢁꢅ4>ꢂ ꢃAꢂ ꢀꢅ4ꢈꢅ+>ꢂ ꢀꢁꢂꢃꢄꢅ ꢆꢇꢈꢄꢅ ꢉꢄ>ꢂ ꢀꢁꢂ>ꢂ ꢋ>ꢂ
STMT?ꢂ(EꢂꢉAꢂꢊ$ꢁ2$ꢁ)2($>ꢂꢇAꢂꢀꢁ04$1ꢁ;>ꢂꢃAꢂꢄꢁ3ꢅ$))ꢁꢅ4>ꢂꢋAꢂꢇꢅ+ꢌ,+>ꢂꢃAꢂꢀꢅ4ꢈꢅ+>ꢂꢀꢁꢂꢃꢄꢅ
ꢆꢇꢈꢄꢅ ꢉꢄ>ꢂ ꢀꢁꢃ>ꢂ >ꢂ TNNS?ꢂ)Eꢂ ꢉAꢂ ꢇ4ꢅ2ꢍ#>ꢂ ꢎAꢂ ꢀAꢂ ꢏAꢂ ꢆAꢂ ꢏꢅ3#ꢁ4>ꢂ ꢐAꢂꢊꢅ23$))-+>ꢂ ꢀꢁꢂꢃꢄꢅ
ꢀꢌꢃꢃꢇꢍꢄ>ꢂ ꢀꢁꢂ>ꢂ#ꢋ>ꢂRNOO?ꢂ*EꢂꢉAꢂꢇ4ꢅ2ꢍ#>ꢂꢆAꢂꢇ$* +ꢁ;Cꢑ4ꢁ+,>ꢂꢆAꢂꢒ4+ꢁ2Cꢓ1ꢌ,$;>ꢂ
ꢏAꢂꢔꢁ1+52>ꢂꢏAꢂꢆAꢂꢏꢅ3#ꢁ4>ꢂꢒAꢂꢏꢅ2ꢁ1ꢅ2>ꢂꢐAꢂꢊꢅ23$))-+>ꢂꢎAꢂꢀ%ꢅ;>ꢂꢀꢁꢂꢃꢄꢅꢆꢇꢈꢄꢅꢉꢄ>ꢂ ꢀꢁꢄ>ꢂ
">ꢂOQNP?ꢂ+EꢂꢄAꢂꢕ,1/$33#ꢅ:ꢅ>ꢂꢖACꢖAꢂꢗ$ꢁ>ꢂꢉACꢕAꢂꢘ4,>ꢂꢗACꢙAꢂꢕ$4>ꢂꢀꢁꢂꢃꢄꢅꢆꢇꢈꢄꢅꢉꢄ>ꢂ ꢀꢀꢄ>ꢂ
ꢊ">ꢂLPQL?ꢂ,EꢂꢄAꢂꢕ,1/$33#ꢅ:ꢅ>ꢂꢖACꢖAꢂꢗ$ꢁ>ꢂꢘAꢂꢔAꢂꢐ,/#:>ꢂꢉACꢕAꢂꢘ4,>ꢂꢗACꢙAꢂꢕ$4>ꢂꢀꢁꢂꢃꢄꢅ
ꢆꢇꢈꢄꢅꢉꢄ>ꢂ ꢀꢁꢀ>ꢂꢊ$>ꢂPSS?ꢂ/EꢂꢒAꢂꢖ#,+">ꢂꢚAꢂꢔꢅꢍ#>ꢂꢀꢁꢂꢃꢄꢅꢆꢇꢈꢄꢅꢉꢄ>ꢂ ꢀꢁꢂ>ꢂ ꢋ>ꢂLNPMM?ꢂ/Eꢂ
ꢊAꢂꢐAꢂꢓꢌꢅ*2>ꢂꢕAꢂꢓAꢂꢔ,1ꢅ)2(:>ꢂꢆAꢂꢓAꢂꢇ4;ꢁ$>ꢂꢉAꢂꢏAꢂꢐꢍ#,*ꢅ(ꢁ1>ꢂꢉꢄꢅꢎꢃꢄꢅꢀꢁꢂꢃꢄꢅꢏꢌꢐꢄ>ꢂ
ꢀꢁ >ꢂ ꢊ!">ꢂ LKSKR?ꢂ 0Eꢂ ꢀAꢂ ꢛAꢂ ꢜ)2,+>ꢂ ꢉAꢂ ꢎAꢂ ꢐ4>ꢂ ꢀAꢂ ꢓAꢂ ꢄ,ꢈꢁ132>ꢂ ꢉAꢂ ꢀAꢂ ꢔ,$2>ꢂ ꢉꢄꢅ ꢎꢃꢄꢅ
ꢀꢁꢂꢃꢄꢅꢏꢌꢐꢄ>ꢂ ꢀꢁꢂ>ꢂꢊ!$>ꢂLNPKQ?ꢂ1EꢂꢄAꢂꢕ,1/$33#ꢅ:ꢅ>ꢂꢘAꢂꢔAꢂꢐ,/#:>ꢂꢉACꢕAꢂꢘ4,>ꢂꢗACꢙAꢂ
ꢕ$4>ꢂ ꢈꢑꢄꢅꢒꢓꢌꢃꢌꢔꢄꢅꢀꢁꢂꢃꢄ>ꢂ ꢀꢀꢅ>ꢂ%>ꢂLMSOAꢂ
FLMGꢂ ꢒ,1ꢂ 2ꢍ1ꢁꢁ+$+"ꢂ ,!ꢂ ,9$ꢌꢅ+32ꢂ ꢅ+ꢌꢂ 234ꢌ$ꢁ2ꢂ ,+ꢂ ꢊ4Cꢍꢅ3ꢅ):232>ꢂ 2ꢁꢁ@ꢂ ꢐ4//,13$+"ꢂ
ꢆ+!,1*ꢅ3$,+>ꢂꢚꢅꢈ)ꢁꢂꢐMꢂ$+ꢂ/ꢅ"ꢁꢂMPꢂꢅ+ꢌꢂꢚꢅꢈ)ꢁꢂꢐNꢂ$+ꢂ/ꢅ"ꢁꢂMQꢂ
FLNGꢂꢅEꢂ ꢉAꢂ ꢐAꢂ ꢅ:+ꢁ2>ꢂ ꢐAꢂ ꢉAꢂ ꢄꢁ33$">ꢂ ꢉAꢂ ꢄAꢂ ꢐꢅ*ꢁ2>ꢂ ꢉAꢂ ꢚ1,33ꢁ1>ꢂ ꢄAꢂ ꢊAꢂ ꢚ#,*/2,+>ꢂ ꢖꢍꢌꢈꢑꢄꢅ
ꢀꢁꢂꢃꢄ>ꢅ ꢁꢅꢄꢄ>ꢂ %>ꢂ LMNR?ꢂ ꢈEꢂ Aꢂ ꢕꢁꢈꢁ)>ꢂ ꢐAꢂ ꢕꢁꢍ3ꢅ1ꢌ>ꢂ ꢏAꢂ ꢃꢅ1*ꢁ+3$ꢁ1>ꢂ ꢈꢑꢄꢅ ꢜꢂꢗꢗꢄ>ꢂ
ꢀꢀꢉ>ꢂ'>ꢂORTRAꢂꢂ
FLOGꢂꢒ,1ꢂ!413#ꢁ1ꢂ,/3$*$;ꢅ3$,+ꢂ,!ꢂ1ꢁꢅꢍ3$,+ꢂꢍ,+ꢌ$3$,+2>ꢂ2ꢁꢁ@ꢂꢐ4//,13$+"ꢂꢆ+!,1*ꢅ3$,+>ꢂ
ꢚꢅꢈ)ꢁꢂꢐOꢂ$+ꢂ/ꢅ"ꢁꢂMQ>ꢂꢚꢅꢈ)ꢁꢂꢐPꢂ$+ꢂ/ꢅ"ꢁꢂMR>ꢂꢅ+ꢌꢂꢚꢅꢈ)ꢁꢂꢐQꢂ$+ꢂ/ꢅ"ꢁꢂMSꢂ
FLPGꢂꢒ,1ꢂ/4)2ꢁꢂ1ꢅꢌ$,):2$2ꢂ,!ꢂꢅ;$1$ꢌ$+ꢁꢂ3,ꢂ"$7ꢁꢂ1ꢅꢌ$ꢍꢅ)ꢂꢍꢅ3$,+ꢂ2/ꢁꢍ$ꢁ2>ꢂ2ꢁꢁ@ꢂꢊAꢂꢇꢅꢁꢈꢁ13>ꢂ
ꢉAꢂꢏꢅ33ꢅ:>ꢂꢏAꢂꢚ,4ꢈꢅ13;>ꢂꢐAꢂꢐ3ꢁꢁ+(ꢁ+>ꢂꢔAꢂꢏ6))ꢁ1>ꢂꢚAꢂꢔꢅ)):>ꢂꢀꢁꢂꢃꢄꢅꢆꢇꢈꢄꢅꢉꢄ>ꢂ ꢀꢀꢇ>ꢂ
ꢊꢊ>ꢂLMTOAꢂ
FLQGꢂꢒ,1ꢂꢅ;$1$ꢌ$+ꢅ3$,+ꢂ,!ꢂ),8ꢂ1ꢁꢅꢍ3$7ꢁꢂ,)ꢁ!$+2ꢂ8$3#ꢂ)ꢅ1"ꢁꢂꢁ9ꢍꢁ22ꢂꢅ*,4+32ꢂ,!ꢂ,)ꢁ!$+2>ꢂ
2ꢁꢁ@ꢂꢅEꢂꢚAꢂ 4+ꢌ)$ꢍ(:>ꢂꢗAꢂꢚ$ꢅ+>ꢂꢘAꢂꢘ.+$"2ꢈꢁ1"ꢁ1>ꢂꢄAꢂꢏꢅ41:ꢅ>ꢂꢉAꢂꢄ,4ꢌꢁ+>ꢂꢔAꢂꢒꢅ+>ꢂꢉꢄꢅ
ꢎꢃꢄꢅ ꢀꢁꢂꢃꢄꢅ ꢏꢌꢐꢄ>ꢂ ꢁꢅꢅꢃ>ꢂ ꢊꢊ&>ꢂ LKRPM?ꢂ ꢈEꢂ ꢏAꢂ ꢓ#*ꢅꢌ$ꢅ+>ꢂ ꢑAꢂ ꢘAꢂ ꢘ#ꢅ1ꢁ>ꢂ ꢉAꢂ ꢏAꢂ
ꢄ$,1ꢌꢅ+>ꢂ ꢓAꢂ ꢛAꢂ ꢘ),+>ꢂ ꢀAꢂ ꢙAꢂ ꢔ,1#ꢅ+$>ꢂ ꢙꢂꢗꢈꢚꢁꢂꢘꢈꢌꢍ>ꢂ ꢀꢀꢁ>ꢂ #%>ꢂ TSTTAꢂ ꢒ,1ꢂ ꢅ+ꢂ
ꢁ!!$ꢍ$ꢁ+3ꢂ *ꢁ3#,ꢌꢂ ,!ꢂ ꢅ;$1$ꢌ$+ꢅ3$,+ꢂ 8$3#ꢂ ꢅ)$/#ꢅ3$ꢍꢂ ,)ꢁ!$+2>ꢂ 2ꢁꢁ?ꢂꢍEꢂ ꢝAꢂ ꢗ4>ꢂ ꢀAꢂ Aꢂ
ꢓ//ꢁ))ꢅ>ꢂ ꢈꢑꢄꢅꢜꢂꢗꢗꢄꢂ ꢀꢀꢄ>ꢂꢊꢋ>ꢂLOTRAꢂ
FRGꢂ ꢒ,1ꢂꢍ,+7ꢁ+3$,+ꢅ)ꢂ*ꢁ3#,ꢌ2ꢂ,!ꢂꢊ4Cꢍꢅ3ꢅ):;ꢁꢌꢂꢅ;$1$ꢌ$+ꢅ3$,+ꢂ,!ꢂꢅ)(ꢁ+ꢁ2>ꢂ2ꢁꢁ@ꢂꢅEꢂꢀAꢂ
ꢓAꢂ ꢛ7ꢅ+2>ꢂ ꢏAꢂ ꢏAꢂ ꢒꢅ4)>ꢂ ꢏAꢂ ꢚAꢂ ꢔ$),ꢌꢁꢅ4>ꢂꢔAꢂ ꢓAꢂ ꢓ+ꢌꢁ12,+>ꢂ ꢀAꢂ ꢏAꢂꢔꢅ1+ꢁ2>ꢂꢉAꢅꢎꢃAꢅ
ꢀꢁꢂꢃAꢅ ꢏꢌꢐA>ꢀ ꢁꢅꢅꢆ>ꢂ ꢊꢊ#>ꢂ PNMS?ꢂ ꢈEꢂ ꢖAꢂ ꢕ$>ꢂ ꢘAꢂ ꢄAꢂ ꢊ,+2ꢁ1>ꢂ ꢛAꢂ ꢑAꢂ ꢉꢅꢍ,ꢈ2ꢁ+>ꢂ ꢉAꢅ ꢎꢃAꢅ
ꢀꢁꢂꢃAꢅꢏꢌꢐA>ꢅꢁꢅꢅꢆ>ꢂꢊꢊ#>ꢂPNMQAꢂꢒ,1ꢂ*ꢁꢍ#ꢅ+$23$ꢍꢂ234ꢌ$ꢁ2ꢂ,!ꢂꢊ4Cꢍꢅ3ꢅ):;ꢁꢌꢂꢅ)(ꢁ+ꢁꢂ
ꢅ;$1$ꢌ$+ꢅ3$,+>ꢂ 2ꢁꢁ@ꢂ ꢍEꢂ ꢖAꢂ ꢕ$>ꢂ ꢄAꢂ ꢙAꢂ ꢝ4ꢅ+>ꢂ ꢛAꢂ ꢑAꢂ ꢉꢅꢍ,ꢈ2ꢁ+>ꢂ ꢉꢄꢅ ꢎꢃꢄꢅ ꢀꢁꢂꢃꢄꢅ ꢏꢌꢐꢄ>ꢂ
FLRGꢂꢒ,1ꢂ2314ꢍ341ꢅ)ꢂꢌꢁ3ꢁ1*$+ꢅ3$,+ꢂ,!ꢂꢆꢊꢂꢅ+ꢌꢂꢆꢋ>ꢂ2ꢁꢁ@ꢂꢐ4//,13$+"ꢂꢆ+!,1*ꢅ3$,+>ꢂ/ꢅ"ꢁ2ꢂ
MTꢂ3,ꢂNMꢂ
ꢁꢅꢅꢇ>ꢂꢊꢊ%>ꢂPSST?ꢂꢌEꢂꢃAꢂꢔ1ꢅ+ꢌ3>ꢂꢏAꢂꢉAꢂꢐ.ꢌꢁ1"1ꢁ+>ꢂꢃAꢂꢇAꢂꢓ+ꢌꢁ122,+>ꢂꢃACꢜAꢂꢑ,11ꢈ:>ꢂ FLSGꢂꢚ#ꢁꢂ1ꢁ"$,2ꢁ)ꢁꢍ3$7$3:ꢂ,!ꢂꢅ;$1$ꢌ$+ꢁꢂ1$+"ꢂ,/ꢁ+$+"ꢂ8ꢅ2ꢂ/ꢁ1!ꢁꢍ3):ꢂꢍ,+31,))ꢁꢌꢂ4+ꢌꢁ1ꢂ
ꢉꢄꢅꢎꢃꢄꢅꢀꢁꢂꢃꢄꢅꢏꢌꢐꢄ>ꢂ ꢀꢀꢀ>ꢂꢊ >ꢂSKLNAꢂ
ꢒ,1ꢂ 1ꢁ7$ꢁ82ꢂ ,!ꢂ ꢅ;$1$ꢌ$+ꢁꢂ 1$+"ꢂ ,/ꢁ+$+">ꢂ 2ꢁꢁ@ꢂ ꢅEꢂ ꢀAꢂ ꢚꢅ++ꢁ1>ꢂꢎꢍꢑꢂꢕꢄꢅ ꢀꢁꢂꢃꢄꢅ ꢖꢍꢗꢄꢅ
ꢆꢘꢄꢅ ꢆꢍꢑꢔꢄ>ꢂ ꢁꢅꢅꢂ>ꢅ !!>ꢂ PTT?ꢂ ꢈEꢂ ꢗAꢂ ꢛAꢂ 4>ꢂ ꢙꢂꢗꢈꢚꢁꢂꢘꢈꢌꢍ>ꢂ ꢀꢀꢂ>ꢂ $ꢋ>ꢂ MRKL?ꢂ ꢍEꢂ ꢏAꢂ
ꢃ$+ꢁ2ꢍ#$>ꢂꢆꢇꢈꢄꢅꢉꢄꢅ ꢈꢑꢄꢅꢀꢁꢂꢃꢄ>ꢂ ꢀꢀꢃ>ꢂOTRTAꢂ
3#$2ꢂꢊ4C*ꢁꢌ$ꢅ3ꢁꢌꢂꢍ,+ꢌ$3$,+Aꢂꢚ,ꢂ3#ꢁꢂꢈꢁ23ꢂ,!ꢂ,41ꢂ(+,8)ꢁꢌ"ꢁ>ꢌ3#$2ꢂ1ꢁ24)3ꢂ$2ꢂ3#ꢁꢂ
!$123ꢂ ꢁ9ꢅ*/)ꢁꢂ ,!ꢂ ꢅꢂ ꢊ4C*ꢁꢌ$ꢅ3ꢁꢌꢂ 1ꢁ"$,2ꢁ)ꢁꢍ3$7ꢁꢂ 1$+"ꢂ ,/ꢁ+$+"ꢂ ,!ꢂ 3#ꢁꢂ 23:1:)ꢂ
ꢅ;$1$ꢌ$+ꢁꢂ8$3#ꢂꢅ;$ꢌꢁꢂ+4ꢍ)ꢁ,/#$)ꢁAꢂꢒ,1ꢂ,3#ꢁ1ꢂꢍ,+7ꢁ+3$,+ꢅ)ꢂ1ꢁꢅꢍ3$,+ꢂꢍ,+ꢌ$3$,+2ꢂ
,!ꢂꢅ;$1$ꢌ$+ꢁꢂ1$+"ꢂ,/ꢁ+$+">ꢂ2ꢁꢁ@ꢂꢐ4//,13$+"ꢂꢆ+!,1*ꢅ3$,+>ꢂꢚꢅꢈ)ꢁꢂꢐTꢂ$+ꢂ/ꢅ"ꢁꢂNRAꢂꢂ
FLTGꢂꢀAꢂꢘꢅ1$)ꢅ>ꢂꢕAꢂꢕꢁ*ꢅ+>ꢂꢄAꢂ Aꢂꢀ,ꢌꢌ>ꢂ ꢈꢑꢄꢅꢜꢂꢗꢗꢄ>ꢂ ꢀꢁꢁ>ꢂꢊ!>ꢂPSNKAꢂ
FMKGꢂꢒ,1ꢂ3#ꢁꢂ,/3$*$;ꢅ3$,+>ꢂ2ꢁꢁ@ꢂꢐ4//,13$+"ꢂꢆ+!,1*ꢅ3$,+>ꢂꢚꢅꢈ)ꢁꢂꢐRꢂ$+ꢂ/ꢅ"ꢁꢂNNAꢂ
FMLGꢂꢀAꢂ ꢕ$>ꢂ ꢀAꢂ ꢎꢅ+">ꢂ ꢕAꢂ ꢙꢅ+">ꢂ ꢗAꢂ ꢕ$4>ꢂ ꢗAꢂ ꢉ$ꢅ+">ꢂ ꢄAꢂ ꢙꢅ+">ꢂ ꢀꢁꢂꢃꢄꢅ ꢆꢇꢈꢄꢅ ꢉꢄ>ꢂ ꢀꢁꢃ>ꢂ >ꢂ
LRLOLAꢂ
FMMGꢂꢘAꢂꢎꢅ*ꢅꢌꢅ>ꢂꢚAꢂꢘ4ꢈ,>ꢂ Aꢂꢚ,(4:ꢅ*ꢅ>ꢂꢚAꢂꢒ4(4:ꢅ*ꢅ>ꢂꢏꢝꢍꢔꢂꢗꢗ>ꢂ ꢀꢀ >ꢂMNLAꢂ
FMNGꢂ ꢚ,ꢂ 3#ꢁꢂ ꢈꢁ23ꢂ ,!ꢂ ,41ꢂ (+,8)ꢁꢌ"ꢁ>ꢂ 3#ꢁ1ꢁꢂ $2ꢂ +,ꢂ ,+ꢁC/,3ꢂ $+ꢌ,)$+ꢁꢂ 2:+3#ꢁ2$2ꢂ !1,*ꢂ
ꢍ,**ꢁ1ꢍ$ꢅ)):ꢂ ꢅ7ꢅ$)ꢅꢈ)ꢁꢂ 23:1ꢁ+ꢁ2Aꢂ ꢒ,1ꢂ ꢅꢂ ,+ꢁC/,3ꢂ $+ꢌ,)$+ꢁꢂ 2:+3#ꢁ2$2ꢂ 8$3#ꢂ ꢍ#$1ꢅ)ꢂ
ꢅ;$1$ꢌ$+ꢁ2ꢂ 7$ꢅꢂ ꢊ4Cꢍꢅ3ꢅ):;ꢁꢌꢂ ꢅ;$1$ꢌ$+ꢁꢂ ,/ꢁ+$+"BꢃꢌCꢍꢅ3ꢅ):;ꢁꢌꢂ $+31ꢅ*,)ꢁꢍ4)ꢅ1ꢂ
ꢅ*$+ꢅ3$,+ꢂ2ꢁ04ꢁ+ꢍꢁ>ꢂ2ꢁꢁ@ꢂꢏAꢂꢘAꢂꢇ#,1ꢅ$>ꢂꢎAꢂꢑꢅ+ꢅ'$>ꢂꢉꢄꢅ ꢈꢑꢄꢅꢀꢁꢂꢃꢄ>ꢂ ꢀꢁꢆ>ꢂ%&>ꢂNSQRA
FSGꢂ
ꢂ
FTGꢂ ꢀAꢂꢓAꢂꢛ7ꢅ+2>ꢂꢏAꢂꢏAꢂꢒꢅ4)>ꢂꢏAꢂꢚAꢂꢔ$),ꢌꢁꢅ4>ꢂꢉꢄꢅꢎꢃꢄꢅꢀꢁꢂꢃꢄꢅꢏꢌꢐꢄ>ꢅꢁꢅꢅꢂ>ꢂꢊꢊ$>ꢂMROMAꢂ
FLKGꢂꢒ,1ꢂꢁ7ꢅ)4ꢅ3$,+ꢂ,!ꢂꢅ;$1$ꢌ$+ꢅ3$,+ꢂ1ꢁꢅꢍ3$7$3:>ꢂ2ꢁꢁ@ꢂꢐ4//,13$+"ꢂꢆ+!,1*ꢅ3$,+>ꢂꢚꢅꢈ)ꢁꢂ
ꢐLꢂ$+ꢂ/ꢅ"ꢁꢂMOꢂ
FLLGꢂꢒ,1ꢂDꢑ OEMꢐMꢜSC*ꢁꢌ$ꢅ3ꢁꢌꢂ +4ꢍ)ꢁ,/#$)$ꢍꢂꢅ;$1$ꢌ$+ꢁꢂ 1$+"ꢂ ,/ꢁ+$+">ꢂ2ꢁꢁ@ꢂ Aꢂꢐ4+>ꢂ ꢔAꢂ
4ꢅ+">ꢂ ꢄAꢂ ꢕ$+>ꢂ ꢊAꢂ ꢎꢅ+">ꢂ ꢙAꢂ ꢗ$ꢅ>ꢂ ꢒꢂꢓꢔꢛꢗꢂꢓꢍꢅ ꢉꢄꢅ ꢈꢑꢄꢅ ꢀꢁꢂꢃꢄ>ꢂ ꢀꢁꢇ>ꢂ ꢊꢊ>ꢂ PMOAꢂ
ꢆ+7,)7ꢁ*ꢁ+3ꢂ ,!ꢂꢊ4C2/ꢁꢍ$ꢁ2ꢂ!,1ꢂ 3#ꢁꢂ ꢅꢍꢍꢁ)ꢁ1ꢅ3$,+ꢂ ,!ꢂ1$+"C,/ꢁ+$+"ꢂ8ꢅ2ꢂ /1,7ꢁꢌꢂ
ꢈ:ꢂ 3#ꢁꢂ ꢍ,+31,)ꢂ ꢁ9/ꢁ1$*ꢁ+3ꢂ 31ꢁꢅ3$+"ꢂ ꢁꢈꢂ 8$3#ꢂ Dꢑ OEMꢐMꢜSꢂ $+ꢂ ꢏꢁꢜ Bꢏꢁꢊꢑꢂ
8$3#,43ꢂꢊ4Cꢍꢅ3ꢅ):23>ꢂ8#$ꢍ#ꢂꢌ$ꢌꢂ+,3ꢂ"$7ꢁꢂ ꢈꢂꢅ!3ꢁ1ꢂLꢂ#ꢂꢅ3ꢂPKꢂHꢊ>ꢂ2ꢁꢁ@ꢂꢐ4//,13$+"ꢂ
ꢆ+!,1*ꢅ3$,+>ꢂꢐꢍ#ꢁ*ꢁꢂꢐQꢂ$+ꢂ/ꢅ"ꢁꢂNSAꢂ
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201900088
European Journal of Organic Chemistry
COMMUNICATION
ꢀꢁ
ꢂꢃꢄꢀꢅꢆꢄꢁꢃꢇ
ꢀꢁꢂꢃꢄꢅꢆꢇꢁꢈꢁꢉꢊꢋꢌꢋꢍꢆ
ꢁꢂꢃꢂꢄꢅꢆꢇꢈꢉꢊꢋꢌꢉꢍꢎꢏꢂꢈꢉꢐꢋꢌꢉ ꢀꢑꢄꢒꢂꢓꢂꢈꢉꢐꢋꢔꢉ
ꢀꢁꢂꢃꢄꢅꢆꢇꢄ ꢄꢀꢁꢂꢃꢄꢅꢆꢇꢄ
ꢇꢇ
ꢇ
ꢎꢏꢐꢑꢉꢄꢆꢒꢐꢂꢓꢈꢌꢏꢂꢁꢉꢌꢔꢁꢈꢌꢏꢂꢆꢏꢕꢆ ꢈꢊꢖꢄꢂꢄꢋꢆ
ꢑꢊꢆꢇꢐꢗꢅꢄꢃꢌꢁꢈꢄꢃꢆꢘꢋꢋꢌꢋꢈꢄꢃꢆꢀꢁꢂꢃꢄꢅꢆ
ꢇꢁꢈꢁꢉꢊꢋꢌꢋꢆ
ꢈꢉꢊꢋꢌ!ꢍꢇꢀꢎꢀꢇꢉꢏꢐꢇꢀꢎꢑꢇꢒꢌꢏꢐꢍꢇꢓꢌ!ꢔꢐꢇꢒꢕꢇꢖꢌꢊꢗꢕꢐꢇꢒ$ꢇꢐꢌ!ꢒꢔꢕꢇꢖ!ꢏꢓ ꢋꢌꢏꢉꢔꢋ%ꢉ ꢋꢌꢏꢇꢌꢖꢇ
ꢌꢔꢕꢖꢋꢏꢍꢇꢖꢕꢉ !ꢊꢋꢏꢘꢇꢀ!ꢎꢗꢕꢐꢋꢉ ꢕꢐꢇꢉꢍꢍꢋꢍ ꢕꢐꢇ ꢉꢏꢐꢕꢗꢇꢓꢉ ꢉꢔ$ꢍꢋꢍꢙꢇꢚ!ꢊ ꢛꢕꢊꢗꢌꢊꢕꢜꢇꢌꢏꢕꢎꢝꢌ ꢇ
ꢋꢏꢐꢌꢔꢋꢏꢕꢇꢍ$ꢏ ꢛꢕꢍꢕꢍꢇ#ꢋ ꢛꢇꢀꢎꢒꢊꢌꢗꢌꢍ $ꢊꢕꢏꢕꢍꢇꢉꢍꢇꢉꢏꢇꢉꢝꢝꢔꢋꢓꢉ ꢋꢌꢏꢇꢓꢌ!ꢔꢐꢇꢒꢕꢇꢉꢓꢛꢋꢕ"ꢕꢐꢙꢇ
This article is protected by copyright. All rights reserved.