Microwave-assisted one-pot quick synthesis of 1-monosubstituted 1,2,3-triazoles from arylboronic acids, sodium azide and 3-butyn-2-ols

Article abstract of DOI:10.1007/s12039-020-01856-4

Abstract: Microwave-assisted one-pot quick synthesis to 1-monosubstituted 1,2,3-triazoles was achieved with good to excellent yields using the widely available arylboronic acids, sodium azide and 3-butyn-2-ols within 15 min. This method features high effi

Full text of DOI:10.1007/s12039-020-01856-4

J. Chem. Sci.
( 2 0 2 0 ) 1 3 2 : 1 5 4
Ó I n d ia n A c a d e m y o f S c i en c es
h t tp s :/ / d o i . o r g/ 1 0 . 1 0 0 7 / s 1 2 0 3 9 - 0 2 0 - 0 1 8 5 6 - 4 Sadhan
(
0
1
2
3
4
5
6
7
8
9
(
)
.
v
o
l
V
)
F
T
3
]
(
0
1
2
3
4
5
6
(
)
.
v
o
l
V
)
REGULAR ARTICLE
Microwave-assisted one-pot quick synthesis of 1-monosubstituted
1,2,3-triazoles from arylboronic acids, sodium azide and 3-butyn-2-
ols
*
Z H O N G L I N D U
,
F
E
N
R
U
I
L
I
,
L
I
L
I
a
n
d
R
A
N
L
I
K u n m i n g M e t a l l u rg y C o l l e g e , N o . 3 8 8 X u e f u R o a d , K u n m i n g 6 5 0 0 3 3 , P e o p l e ’ s R e p u b l i c o f C h i n a
E - m a i l : 5 5 1 9 9 0 1 0 1 @ q q . c o m
M S r e c e i v e d 1 6 A u gu s t 2 02 0 ; r e v i s e d 3 0 S e p t e m be r 2 0 2 0; a c c e p t e d 3 O c t o b e r 2 0 2 0
Abstract. M i c r o w a v e - a s s i s t e d o n e - p o t q u i c k s y n t h e si s t o 1 - m o n o s u b s t i t u t e d 1 , 2 , 3 - t r i a z o le s w a s a ch i ev ed
w i t h g o o d t o e x c e l l e n t y i e l d s u s i n g t h e w i d e l y a v a il a b l e a r y lb o r o n i c a c i d s , s o d i u m a z i d e a n d 3 - b u t y n - 2 -o l s
w i t h in 1 5 m i n . T h i s m e t h o d f e a t u r e s h i g h e f fi c i e n t a n d f a c il e a s o r g a n i c a z i d e s , a c e t y l e n e g a s a n d h ar s h
c o nd i t i o n s w e re a v o i d e d .
Keywords. m i c ro wa v e -a s s i s t e d ; o n e - p o t ; 1 - m o n o s u b s t i t u t e d 1 , 2 , 3 - t r i a z o l e ; 3 - b u t y n - 2 - o ls .
1
3
1. Introduction
5 - t r i s u b s i t u t e d 1 , 2 , 3 - t r i az o l es h a v e b e e n a l so s y n -
t h es i z ed m ai n l y t h ro u g h a t h re e - co mp o n e n t s y st em .
W h i l e 1 - m o n o s u b s t i t u t e d 1 , 2 , 3 - t r i az o l e d e r i v a t i v e s,
a n o t h e r p a r t i c u l ar b r a n c h o f t h i s h e t e r o c y c l e s s h o w
v a r i o u s h i g h v a l u es , m ai n l y o w i n g t o i t s b r o a d b i o -
l o g i c a l a ct i v i t i e s ( Fi g u r e 1 ) . T h u s , t h e e x p l o r at i o n s f o r
t h e c o n s t r u c t i o n s a t t r a c t m u c h a t t e n t i o n r e c en t l y .
A c et y l e n e g a s i s t h e m o s t a ck n o w l e d g ed s u b st r at e t o
s e r v e a s a p a r t n e r o f t h e C u A A C r ea c t i o n w i t h o r g a n i c
a zi d e s t o g e n e r at e 1 - m o n o s u b s t i t u t e d 1 , 2 , 3 - t r i a zo l e s,
1 , 2 , 3 - T r i az o l es a re a n i m p o r ta n t k i n d o f h e t e r o c y c l i cs
w i d el y a p p l i e d i n m a ny fi e l d s s u c h a s b io l o g i ca l s c i -
1
e n c e , m at e r i a l fi e l d , m e d i c i n a l c h e m is tr y a n d s y n -
2
3
4
t h e t i c m e t h o d o l o g i e s . P a rt i c u la r ly i n r e c e n t y e a rs ,
t h e y h a v e p l ay e d i nc re a s in g ly i m p o rt a nt r o l e s i n
c l in i c a l a n d c o m m e r c i a l d r u gs s u c h a s I D O ( i n -
5
d o l e a m in e 2 , 3- di o x y g e n a se ) i nh ib i to rs , a n t ib i o t i cs ,
6
7
H D I s ( h i s t o n e d e a c e t y la s e i nh ib i to rs ) a n d a n t i v i r al
8
1 4
d
r
u
g
s
(
F
i
g
u
r
e
1
)
.
w h i ch w a s fi rs t r ep o r t e d b y L i an g g r o u p . A d d i t i o n -
T h o u g h 1 , 2 , 3 - tr i a z o l e s w e r e f o u nd m o re t h a n 1 0 0
y e a r s a g o , e f fi c i e n t s t r a t e g ie s f o r t he s y nt h e s i s h a v e
b e e n e x p l o r ed o n l y i n r e c e nt d e c a d e s . T h e fi r s t m et h o d
t o c o n s t r u c t t h e 1 , 2 , 3 - t ri a z o l e r in g w a s H u i s g en
d i p o l a r c y c l o ad di ti o n t hr ou g h t h e t he rm a l p r o ce s s ,
g i v i n g 1 , 4- a n d 1 , 5- di s u b s t it ut e d r e g i o is om e r s w i t h o u t
a l l y , a ce t y l e n e d e r i v a t i v e s ( s u c h a s t r i me t h y l s i l y -
l a c e t y l e n e , e t h y n y l t r i b u t y l t i n, s o d i u m a c e t y l i d e ,
c al c i u m c ar b i d e , p r o p i o l i c a ci d , a n d p r o p a r g y l a l co h o l )
a n d v i n y l c o m p o u n d s ( s u c h a s v i n y l a ce t at e , v i n y l
e t h e r s , v i n y l a mi n e s , a n d v i n y l s u l f o x i d e s ) h a v e b e e n
p r o v e d t o b e r e l i a b l e a l t e r n a t i v es t o s y n t h e s i z e t h e
9
1
5
r e g i o s e l e ct i vi t y . A t t he b e gi n ni n g o f t h i s c en t u r y ,
1 0
S h a r p l e s s g r o u p a c hi e v e d a c o pp e r -c a ta lyz ed 1 , 3 -
p
r
o
d
u
c
t
s
.
I
n
m
o
s
t
o
f
t
h
e
a
b
o
v
e
m
e
t
h
o
d
s
,
a
c
e
t
y
l
e
n
e
g a s , v o l a t i l e t o x i c o r g a n i c a zi d e s a n d / o r h a r s h c o n d i -
t i o n s a r e i n v o l v e d , w h i ch l e a d s t o s o m e d r a w b ac k s o f
s a f et y c o n c e rn s a n d / o r i n co n v e n i e n c e i n t h e p r o c e ss o f
m an i p u l a t i o n s .
d i p o l a r c y c l o a d d it i on r e a c t io n ( C uA A C ) b e t we e n t e r -
m i n al a l k y n e s a n d a z i de s , r e a c hi n g t h e r e g i o s e l e ct i v e
c o ns t r u ct i o n o f t h e 1 , 4 - d is u b s t it u te d 1 , 2 , 3 - t r i az o l es .
T h i s m e t h o d i s v e r y v i g o r o u s a n d l e d t o m a n y o t h e r
E n l i g h t e n e d b y J i an g ’ s r e ce n t w o r k , i n w h i c h
2 - m et h y l -3 - b u t y n- 2 - o l w a s e mp l o y ed a s a n e xc e l l en t
a l k y n e s o u r ce f o r t h e c o n s t r u ct i o n o f 1 - m o n o su b st i -
1
1
s i mi l a r a p p r o a c h e s s u b s e q ue nt l y . M e a n w h i l e , t h e
s y n t h e s i s f o r 1 , 5 - di s u bs it u te d 1 , 2 , 3 -t ri a z o le s w e r e
1 5 i
r e p o r t e d , i n w h i c h r u t he ni u m , e r b iu m , o r b a s e w e r e
1 2
t u t e d 1 , 2 , 3 - t r i a z o l e s w i t h o r g a n i c a zi d e s , a n d b y t h e
r e p o r t s t h at a ry l b o ro n i c a ci d a n d s o d i u m a zi de c o u l d
u s u a l l y a p p l i e d a s t h e c a t a l ys t.
L a t e l y , 1 , 4 ,
* F o r c o r re s p o n d e n c e
Electronic supplementary material: The online version of this article (https://doi.org/10.1007/s12039-020-01856-4) contains
supplementary material, which is available to authorized users.

1
5
4
P
a
g
e
2
o
f
7
J. Chem. Sci.
(
2
0
2
0
)
1
3
2
:
1
5
4
O
S
N
O
N
H
O
N
NH
HO
RO
H
N
N
N
OH
NH
(CH2)n
N
N
O
N
N
R
N
O
COOH
R=H, Cl, Br
IDO inhibitor
n=4-8
HDIs
Antibiotic
N
N
N
N
N
N
O
CO2Et
F3C
AcO
O
AcO
Antiviral drug
OAc
O
Anti breast cancer
Figure 1. E x a m p l e s o f b i o l o g y i n h i b i t o r s .
1 6
2
.
2
G
e
n
e
r
a
l
s
y
n
t
h
e
t
i
c
p
r
o
c
e
d
u
r
e
s e r v e t o s y n t he s i ze o rg a n ic a z i de s , w e e n v i s io n t h es e
t h r e e s t a r t i ng m a t e ri a ls c o u l d f o r m t he 1 -m o no s u b s t i -
t u t e d 1 , 2 , 3 - t ri az ol e s i n a m o re s a fe a n d f a c i l e o n e - p o t
p r o c e d u r e ( S c h e m e 1 ) .
A r y l b o r o n i c a ci d 1 ( 0 . 3 m mo l ) , b u t - 3 - y n - 2 - o l 2
( 0 . 3 6 m mo l ) , s o d i u m a zi d e 3 ( 0 . 3 6 m mo l ) , K OH
( 0 . 9 m mo l ) , C u I ( 0 . 0 1 5 m mo l ) , N a A s c ( 0 . 0 3 m m o l ) ,
a n d P h M e - H O ( 2 m L , 5 : 1 i n v o l u m e ) w e r e a d d e d t o a
2
2. Experimental
m i c ro w a v e r e ac t i o n t u b e . T h e m i x t u r e w a s c o n d u c t e d
u n d er m i c ro w a v e a t 8 0 °C f o r 1 5 m i n . A f t er t h e
2 . 1 Materials and methods
r ea c t i o n c o m p l e t e d b y T L C a n a l y s i s , H O ( 2 5 m L )
2
w a s a d d e d t o t h e m i x t u r e a n d t h e s y s t e m w a s e x t r a c t e d
w i t h E t OA c ( 3 9 2 0 m L ) . T h e c o m b i n e d o r g a n i c l a y e r
w a s w a s h e d w i t h b r i n e ( 3 9 5 m L ) , d r i e d w i t h
N a S O , a n d c o n c e n t r a t e d u n d e r r e d u c ed p r e ss u r e t o
a ff o r d t h e c r u d e p r o d u ct . P u r i fi ca t i o n b y c o l u m n
c h r o m at o g r a p h y o n s i l i c a g e l w i t h E t O A c- P E ( 1 : 5 )
a ff o r d ed t h e d e s i re d p r o d u ct 4.
A l l c o m m e r c i all y a v a i l a b l e r e a g e n t s a n d s o l ve n t w e r e
o b t a i n e d f r o m t h e c o m m e rc i a l p ro v i de rs ( A la d d i n a n d
B o k a c h e m , C h i n a ) a n d u s e d w i t h o u t f u r th e r p u r i fic a -
t i o n . A l l t h e r e a c t io n s w e r e c o n d u c t e d u s i n g C E M
D i s c o v e r - S P m i c r o w a v e i n s tr u m e n t . N M R s p e c t r a
w e r e r e c o r d e d w i t h a B r u k e r A C F 4 0 0 a n d A R X 6 0 0 o r
2
4
5 0 0 s p e c t r o m e t e r i n C D C l w i t h T M S a s a n i n t e rn al
3
s t an d a r d . A l l r e a c t io ns w e r e m o ni t or e d b y T L C a n a l -
y s i s w i t h H u a n g h a i GF 2 5 4 s i l i c a g e l -c oa te d p l at es .
C o l u m n c h r o m a t o g ra p h y w a s c o n d u c t e d u s i n g 3 0 0 t o
4 0 0 m es h s i l i c a g e l a t m e di u m p re s s u r e .
3. Results and Discussion
I n o u r i n i t i al s t u d y , p h e n y l b o ro n i c a ci d ( 1a) ,
2 - m et h y l b u t -3 - y n- 2 - o l ( 2a) , a n d s o d i u m a zi d e 3 w er e
c h o s e n a s s t ar t i n g m at er i al s f o r o p t i m i z a t i o n o f t h e
r ea c t i o n c o n d i t i o n s . 3 5 % Y i e l d o f p r o d u c t 1 - p h e n y l -
1 H - 1 , 2 , 3 - t r i az ol e 4a w a s o b t a i n e d w h e n t h e r e a ct i o n
w a s c at a l y z e d b y C u I ( 5 % ) - N aA s c (1 0 % ) , u s i n g K OH
( 2 e q u i v . ) a s t h e b a s e , a n d P h M e - C H O H ( 1 : 3 , V : V ) a s
3
t h e s o l v e n t u n d er 8 0 °C ( T a b l e 1, e n t r y 1 ) . T h e c o m -
p o n e n t r a t i o o f t h e m i x t u r e s o l v e n t a f fe c t e d t h e r e a c-
t i o n s a n d P h M e - CH O H i n 3 : 1 c o u l d d e l i v e r a y i e l d o f
3
5 3 % ( T a b l e 1 , e n t r y 3 ) . R ep l a ci n g C H O H w i t h H O
3
2
i n t h e s o l v e n t m i x t u r e c o u l d r em a r k ab l y r a i s e t h e
y i el d a n d e x c el l e n t y i el d o f 7 8 % w a s o b t a i n e d w h en
Scheme 1. 1 - m o n o s u b s t i t u t e d 1 , 2 , 3 -t ri a z o l e s c o n s t r u c -
t io n s u s i n g 3 - b u t y n - 2 - o l s .

J. Chem. Sci.
(
2
0
2
0
)
1
3
2
:
1
5
4
P a g e 3 o f 7
1
5
4
a
Table 1 O p t i mi z at i o n o f r e a c t i o n c o n d i t i o n s
b
E
n
t
r
y
B
a
s
e
(
e
q
u
i
v
.
)
S
o
l
v
e
n
t
T
e
m
p
.
T
i
m
e
4a ( % )
1
2
3
4
5
6
7
8
K OH ( 2 )
K OH ( 2 )
K OH ( 2 )
K OH ( 2 )
K OH ( 2 )
K OH ( 2 )
K OH ( 2 )
K OH ( 3 )
K OH ( 4 )
K OH ( 3 )
K OH ( 3 )
K OH ( 3 )
N a O H ( 3 )
C s O H ( 3 )
K C O ( 3 )
T o l u e n e / C H O H ( 1 :3 )
3
T o l u e n e / C H O H ( 1 :1 )
3
T o l u e n e / C H O H ( 3 :1 )
3
T o l u e n e / H O ( 3 :1 )
2
T o l u e n e / H O ( 4 :1 )
2
T o l u e n e / H O ( 5 :1 )
2
T o l u e n e / H O ( 6 :1 )
2
T o l u e n e / H O ( 5 :1 )
2
T o l u e n e / H O ( 5 :1 )
2
T o l u e n e / H O ( 5 :1 )
2
T o l u e n e / H O ( 5 :1 )
2
T o l u e n e / H O ( 5 :1 )
2
T o l u e n e / H O ( 5 :1 )
2
T o l u e n e / H O ( 5 :1 )
2
T o l u e n e / H O ( 5 :1 )
2
8
0
°
C
1 2 h
1 2 h
1 2 h
1 2 h
1 2 h
1 2 h
1 2 h
1 2 h
1 5 m i n
1 5 m i n
1 5 m i n
1 5 m i n
1 5 m i n
1 5 m i n
1 5 m i n
1 5 m i n
1 5 m i n
1 5 m i n
1 5 m i n
3 5
4 3
5 3
6 0
6 6
7 8
7 5
8 2
8 2
8 9
8 0
8 3
6 3
6 6
4 0
–
8 0 °C
8 0 °C
8 0 °C
8
0
°
C
8 0 °C
8
0
°
C
8
0
°
C
9
8 0 °C - M W
8 0 °C - M W
9 0 °C - M W
7 0 °C - M W
8 0 °C - M W
8 0 °C - M W
8 0 °C - M W
8 0 °C - M W
8 0 °C - M W
8 0 °C - M W
8 0 °C - M W
1 0
1 1
1 2
1 3
1 4
1 5
1 6
1 7
1 8
2
3
K OH ( 3 )
K OH ( 3 )
K OH ( 3 )
K OH ( 3 )
T o l u e n e
D M S O
D M F
4 2
3 6
6 0
c
1 9
T o l u e n e / H O ( 5 :1 )
2
a
T h e r e a c t i o n c o n d i t i o n s a r e a s f o l l o w s : p h e n y l b o r o n i c a c i d 1a ( 0 .3 m m o l ) , 2 - m e t h y l b u t- 3 - y n -
2 - o l 2a ( 0 . 3 6 m m o l ) , s o d i u m a z i d e 3 ( 0 .3 6 m m o l ) , b a s e , C u I ( 0 .0 1 5 m m o l ) , N a A s c ( 0 .0 3
m m ol ) , a n d s o l v e n t ( 2 m L ) .
b
I s o l a t e d y i e l d .
c
W
i
t
h
o
u
t
s
o
d
i
u
m
a
s
c
o
r
b
a
t
e
.
P h M e - H O i n 5 : 1 w a s u s e d ( T a b le 1 , e n t ri e s 4 – 7 ) . W e w h e n t h e r ea c t i o n w a s c o n d u ct e d w i t h o u t i t ( Ta b l e 1 ,
2
t h e n e x p l o r ed t h e l oa di n g a m ou n t o f K O H a n d f o u n d e n t r y 1 9 ).
t h e r e a c t i o n p r e f e rr e d t o 3 e q u i v a l e n ts o f K O H , g e n -
W i t h t h e o p t i m i z e d c o n d i t i o n s i n h a n d , t h e o n e - p o t
e r a t i n g a n e x c e l l e n t 8 2 % y ie ld w h il e o v e r m u c h b a s e p r o c e s s e s w e re e x p l o r ed w i t h a r an g e o f a r y l b o r o n i c
s e em e d n o o b v i o u s e f f e c t s ( T a b le 1, e n t ri e s 8 – 9 ) . T o a ci d s (1) w i t h 2 - m et h y l b u t -3 -y n- 2 - o l (2a) a n d s o d i u m
o u r d e l i g h t , t h e t a r g e t m o le c u le w a s r e m a r k ab l y a zi d e ( 3) i n m i x t u r e s o l v e n t o f P h C H - H O , g e n er a t i n g
3
2
i n c r e as e d t o 8 9 % y ie ld w h e n m i c r o w a v e ( MW ) w a s 1 - m o n o s u b s t i t u t ed 1 , 2 , 3 - t r i a z o l e s ( 4) w i t h g o o d t o
e m p l o y ed i n a 1 5 m i n -a s s is t i n g i ns te a d o f t ra d i t i o n a l e x c el l e n t y i el d s . A s s h o w n i n T a b l e 2 , t h e r e ac t i o n s o f
h e a t i n g ( T a b l e 1, e n t ri e s 1 0 ) . T h ro u g h m i c r o w av e, t h e a r y l b o ro n i c a ci d s u b s t r a t e s c o n t ai n i n g e l e c t r o n - d o n at -
r e a c t i o n t e m p e r at u re a l s o h a d a d i s ti n c t i nfl ue n ce o n i n g g r o u p ( s u c h a s – C H , – O C H ) o r e l e c t r o n - wi t h -
3
3
t h i s c o n v e r s i o n a n d 9 0 °C o r 7 0 °C i s u n f a v o ra b l e t o d r a w i n g g r o u p ( s u c h a s – S O N H , – N O , – F , – C l , –
2
2
2
t h e c o mb i n a t i o n ( T a bl e 1 , e n t ri e s 1 1 – 1 2 ) . B a s es l i k e B r) c o u l d a l l g o s m o o t h l y ( T a b l e 2 , 4a– 4o) . I t i s w o r t h
N a O H , C s O H a n d K C O w e r e a l s o s c re e n e d t o b e n o t i n g t h at s u l f o a mi d o a n d - Br w e re w e l l - t o l e r a t e d i n
2
3
m u c h l e s s e f fi c i e n t ( T a b l e 1 , e n t ri e s 1 3 – 1 5 ). O t h er t h e s y s t e m a n d a g o o d y i el d w a s g e n e r at ed ( T a b l e 2 ,
k i n d s o f s o l v en t s i nc lu d i n g P h M e , D M S O a n d D M F 2g, 2o) , w h i ch a f fo rd s p o t e n t i al a p p l i c at i o n s o f l a t e -
o n l y p r o d u c e d u n s a t i s f a c t o r y y i e ld s ( T a b le 1 , e n t r i es s t ag e m o d i fi c a t i o n s . I t w a s o b s er v e d t h at e l e c t r o n - d o -
1 6 – 1 8 ) . T h e s o d i u m a s c o rb a t e p l a ye d a v i t a l r ol e i n t h e n a t i n g s u b s t i t u e n t s a r e b e n e fi ci al t o t h i s o n e - p o t
s y s t e m a s a n o b v i ou s d e c l i ne o f t h e y i e ld c a m e o u t c o m b i n at i o n l e a d i n g h i g h e r y i el d s , a n d e l ec t r o n -

1
5
4
P
a
g
e
4
o
f
7
J. Chem. Sci.
( 2 0 2 0 ) 1 3 2 : 1 5 4
a , b
Table 2. S u b s t r a t e s s c o p e
a
R e a ct i o n c on di t io n s : T h e r e a c t i o n c o n d i t i o n s a r e a s f o ll o w s: a r y lb o r o n i c a c i d 1 ( 0 .3 m m o l ) , 2 - m e t h y l b u t - 3 - y n- 2 -o l 2a
( 0. 3 6 m m o l ) , s o d i u m a z i d e 3 ( 0 . 3 6 m m o l ), K OH ( 0 .9 m m o l ) , C u I ( 0 .0 1 5 m m o l ) , N a A s c ( 0 .0 3 m m o l ) , a n d P h M e - H O
2
b
(
2
m
L
,
5
:
1
i
n
v
o
l
u
m
e
)
w
e
r
e
m
i
x
e
d
a
n
d
s
t
i
r
r
e
d
a
t
8
0
°
C
b
y
m
i
c
r
o
w
a
v
e
f
o
r
1
5
m
i
n
.
I
s
o
l
a
t
e
d
y
i
e
l
d
.
w i t h d r a w i ng g r o u p s s e e m e d a b i t u n f a v o ra b l e t o t h i s a ce t o p h e n o n e 5 c o u l d b e i s o l a t e d w h e n 2 - p h e n y l b u t - 3 -
p r o c e s s ( T a b l e 2 , 4b–4f vs 4g–4o) . M or e o v e r , y i el d s y n - 2 - o l w a s e mp l o y e d a s t h e a ce t y l e n e s o u r c e
f r o m s u b s t r a t e s w i t h a s u b s t it u e nt o n para- p o s i t i o n a r e ( T a b l e 3, e n t r y 3 ) .
h
i
g
h
e
r
t
h
a
n
t
h
a
t
f
r
o
m
o
t
h
e
r
c
a
s
e
s
(
T
a
b
l
e
2
,
4
d
v
s
4
b
T o g a i n f u r t h er m ec h a n i s t i c i n s i g h t i n t o t h e r e a c-
a n d 4c, 4f vs 4e, 4i vs 4h, 4k vs 4j, 4n vs 4l a n d 4n) . t i o n s , s o m e c o n t ro l e x p e r i m en t s w e r e c ar r i e d o u t
N e x t , t h e s c o p e o f b u t -3 - y n - 2 o l s w a s e x pl o r e d a s ( Sc h e m e 1 ) . F i r s t l y , p- t o l y l b o r o n i c a ci d 1d a n d
s h o w n i n T a bl e 3 . 3 -M e th y l p en t - 1- y n - 3 - o l (2b) , s o d i u m a zi d e 3 c o u l d s m o o t h l y c o m b i n e i n t o 1 - az i d o -
3 - e t h y l pe nt - 1- y n -3 - o l ( 2c) a n d 2 - p he n y lb ut - 3 - yn - 2 - o l 4 - m et h y l b e n z en e 6 w i t h a n e x c el l e n t y i el d o f 9 3 %
(2d) c o u l d a l l u n d e r g o t h e t ra ns fo r m a t i o n s m o o t h l y u n d e r t h e s t an d ar d c o n d i t i o n s ( Sc h e m e 2 , E q . 1 ) .
w i t h p h e n y l b o r on ic a c i d (1a) , d e l iv e r in g c o r re s p o n d - M e a n w h i l e , t h e g e n e r at ed i n t e rm e d i at e
i n g m o no - s ub st i tu t e d 1 , 2 , 3 -t r i a z o l e ( 4a) . N o t ab l y , 2 - m et h y l b u t -3 - y n- 2 - o l 2 c o u l d f o r m t h e t a r g e t
6
a
n
d

J. Chem. Sci.
(
2
0
2
0
)
1
3
2
:
1
5
4
P
a
g
e
5
o
f
7
1
5
4
a
,
b
Table 3. S u b s t r a t e s s c o p e
c
Entry
2
1
2
3
Y
i
e
l
d
7
8
7
4
8
2
a
R e a ct i o n c o nd i t i o n s : T h e r e a c t i o n c o n d i t i o n s a r e a s f o ll o w s : p h e n y l b o r o n i c a c i d 1a ( 0 .3 m m o l ) , b u t - 3 - y n - 2 - o l 2 ( 0. 3 6
m m ol ) , s o d i u m a zi d e 3 ( 0 . 3 6 m m o l ) , K OH ( 0 . 9 m m o l ) , C u I ( 0 .0 1 5 m m o l ) , N a A s c ( 0 .0 3 m m o l ) , a n d P h M e - H O ( 2 m L , 5 :1
2
i n v o l u me ) w e r e m i x e d a n d s t i rr e d a t 8 0 °C b y m i c r o w a v e f o r 1 5 m i n .
I so l at ed y i el d .
b
c
B
y
-
p
r
o
d
u
c
t
o
f
a
c
e
t
o
p
h
e
n
o
n
e
5
w
a
s
i
s
o
l
a
t
e
d
.
4. Conclusions
I n c o n c l u s i o n , w e h a v e d e m o n s t ra t e d t h e m i c r o w a v e -
a s s i s t e d f a ci l e , q u i c k a n d h i g h l y e f fic i e n t o n e - p o t
s y n t h e s i s o f 1 - m o n o s u b s t i t ut e d 1 , 2 , 3 - t r i a z ol e s b y
u s i n g t h e w i d el y a v a i l a b l e a r y l b o ro n i c a ci d s , s o d i u m
a zi d e a n d b u t y n - 2 - o l s w i t h g o o d t o e x c el l e n t y i e l d s .
Supplementary Information (SI)
Scheme 2. C o n t r o l e x p e ri m e n t s .
A l l t h e s p e c tr a a r e a v a i l a b l e a t w w w . ia s. a c . i n / c h e m s c i .
Acknowledgements
W e a r e g r a te f u l f o r t h e fi n a n c ia l s u p p o r t p r o v i d e d b y t he
N a t u r a l S c i e n c e F o u n d a t io n o f Y u n n a n E d u c a t i o n D e pa r t-
m e n t ( N o . 2 0 2 0 J 0 7 6 8 ) .
Scheme 3. G r a m s c a l e e x p e r i m e n t .
References
1 . ( a ) L u G , L i X , M o h a m e d K , W a n g D a n d M e n g F 2 01 9
D e s i g n , s y n t h e s i s a n d b i o l o g i c a l e v a l u a t i o n o f n o ve l
u r a c i l d e r i v a t i v e s b e a r i n g 1 , 2 , 3 - tr ia z o l e m o i e ty a s
t h y m i d y l a t e s y n t h a s e ( T S ) i n h i b i t o r s a n d a s p o t e n ti a l
a n t i t u m o r d r u g s Eur. J. Med. Chem. 171 2 8 2 ; ( b ) T hi r u-
m u r u g a n P , M a t o s i u k D a n d J o z w ia k K 2 0 1 3 C l i c k
c h e m is t r y f o r d r u g d e v e lo p m e n t a n d d i v e r s e c h em i ca l -
b i o l o g y a p p li c a t i o n s Chem. Rev. 113 4 9 0 5
2 . ( a ) L i u Y , H e C , T a n g Y , I m l e r G , P a r r i s h D a nd
S h r e e v e J 2 0 1 9 T e t r a z o ly l a n d d i n i t r o m e t h y l g ro up s
w i t h 1 , 2 , 3 - t r i a z o l e l e a d t o p o l y a z o l e e n e r g e t i c m a te r ia l s
Dalton Trans. 48 3 2 3 7 ; ( b ) C h u C a n d L i u R 2 01 1
A p p li c a t i o n o f c l i c k c h e m is t r y o n p r e p a r a t io n o f
m o l e c ul e 4d i n a y ie ld o f 9 0 % u n d e r t h e s a m e c o n -
d i t i on s ( S c h e me 2, E q . 2 ) . I t w a s i m p l i e d t ha t t h e a ry l
a zi d e s h o u l d g e n e r a t e fi r s t l y a s t h e i nt e r m e d i a t e , w h i ch
t h e n u n d e r g o e s a c y c l o a d di ti o n p r o c e s s t o d e l i v e r t h e
m o n o su bs t i t u t e d 1 , 2 , 3 -t r i a z o l e a c c o m p a n i ed b y
r e l e a s i ng a m o l e c u le o f k e t o n e a s a b y - p r o d u c t .
T o t e s t t h e s c a l a b i l it y o f t h e c u r re n t m e th o d , t h e
g r a m s c a l e r e a c t io n o f p h e n y l b o r o n i c a ci d 1a
( 4 . 0 m m o l , 1 . 07 9 g ) a s t he s t a rt i ng m a te ri a l s w a s
c ar r i ed o u t u n d e r t he s t a nd a rd c o n d i ti o n s , a n d t h e
p r o d u c t 2a w a s i s ol a t e d i n 7 8 % y i e ld ( S c h e m e 3 ) .

1
5
4
P
a
g
e
6
o
f
7
J. Chem. Sci.
( 2 0 2 0 ) 1 3 2 : 1 5 4
s e pa r a t i o n m at e r i a l s f o r l i q u i d c h ro m a t o g r a p h y Chem.
Soc. Rev. 40 2 1 7 7
3 . ( a ) B o zo r o v K , Z h a o J a n d A i s a H 2 0 1 9 1 , 2 , 3 -T r i a z o l e -
c o nt a in i n g h y b r i d s a s l e a d s i n m e d i c i n a l c h e m i s t r y : A
r e ce n t o v e r v ie w Bioorg. Med. Chem. 27 3 5 1 1 ; ( b ) J o -
C h r i s t o d o u l o u M , F u m a g a l l i G , et al. 2 0 1 7 T h e 1 ,2 , 3-
t r i a z o l e r i n g a s a b i o i s o s t e r e i n m e d i c i n a l c h e m i s t r y
Drug Discov. Today 22 1 5 7 2
9 . H u is g e n R 1 9 6 1 c e n te n a r y l e c t u r e . 1 , 3 - D i p o la r c y cl o ad -
d i t io n s Proc. Chem. Soc. 3 5 7
h
a
n
s
s
o
n
J
,
B
e
k
e
-
S
o
m
f
a
i
T
,
S
t
a
l
s
m
e
d
e
n
A
a
n
d
K
a
n
n
N
1
0
.
R
o
s
t
o
v
t
s
e
v
V
,
G
r
e
e
n
L
,
F
o
k
i
n
V
a
n
d
S
h
a
r
p
l
e
s
s
K
2
0
0
2
2 0 1 6 R u th en i u m -c a t a l y z e d a z i d e a l k y n e c y c l o a d d i t io n
r e ac t i o n: s c op e , m e c h a n i s m , a n d a p p l i c a t i o n s Chem.
Rev. 116 1 4 7 2 6 ; ( c ) S h e n g C a n d Z h a n g W 2 0 1 1 N e w
A s t e p w i s e H u is g e n c y c lo a d d i t io n p r o c e s s : c o p pe r (I ) -
c a t a l y z e d r e g io s e l e c t iv e ‘‘ l i g a t i o n ’’ o f a z i d e s a n d t er m i-
n a l a l k y n e s Angew. Chem. Int. Ed. 41 2 5 9 6
l
e
a
d
s
t
r
u
c
t
u
r
e
s
i
n
a
n
t
i
f
u
n
g
a
l
d
r
u
g
d
i
s
c
o
v
e
r
y
C
u
r
r
.
M
e
d
.
1
1
.
(
a
)
N
e
t
o
J
a
n
d
Z
e
n
i
G
2
0
2
0
A
d
e
c
a
d
e
o
f
a
d
v
a
n
c
e
s
i
n
t
h
e
Chem. 18 7 3 3 ; ( d ) J i a n g Y a n d K u a n g C 2 0 1 3 R e c e n t
a d va n c e s i n t h e s y n t h e s i s o f 1 - m o n o s u b s t i t u t e d 1 , 2 , 3 -
t r i a zo l e s Mini-Rev. Med. Chem. 13 7 1 3
r e a c t io n o f n i t r o g e n s o u r c e s a n d a l k y n e s f or t he
s y n t h e s i s o f t r i a z o l e s Coordin. Chem. Rev. 409
2 1 3 2 1 7 ; ( b ) A u ta d e S a n d A k a m a n c h i K 2 0 1 9 S u l f at e d
t u n g s t a t e a h e t e r o g e n e o u s a c i d c a t a l y s t f o r s y n t h es i s o f
4 - a r y l - N H - 1 ,2 ,3 - t r i a z o l e s b y 1 , 3 - d i p o l a r c y c lo ad d i t i on
o f n i tr o o l e fi n s w i t h N a N Synth. Commun. 49 1 94 7;
3
( c ) J i a n g Y a n d K u a n g C 2 0 1 2 S y n t h e s i s o f 1 ,2 , 3-
t r i a z o l e d e r iv a t i v e s Prog. Chem. 24 1 9 8 3
4 . ( a ) C h en K , B ar v e I a n d S u n C 2 0 2 0 C a t a l y s t -c o n t r o ll e d
r e g i o se l ec t i ve s y n t h e s i s o f b e n z o t r i a z o l o d i a z e p i n - 7 -
o n e s a n d b en zo t r i a z o l o d i a z o c i n - 8 - o n e s Org. Lett. 22
4 2 8 ; ( b ) V i r a n t M a n d K o s m r l j J 2 0 1 9 A ry l a t i o n o f c l i c k
t r i a zo l e s w i t h d i a r y l i o d o n i u m s a l t s J. Org. Chem. 84
1
4
0
3
0
;
(
c
)
R
e
n
Y
,
L
i
u
Y
,
G
a
o
S
,
D
o
n
g
X
,
X
i
a
o
T
a
n
d
1
2
.
(
a
)
K
w
o
k
S
,
F
o
t
s
i
n
g
J
,
F
r
a
s
e
r
R
,
R
o
d
i
o
n
o
v
V
a
n
d
F
o
k
i
n
J i an g Y 2 0 2 0 P a l l a d i u m - c a t a l y z e d s e l e c t i v e o r t h o C - H
a lk o x y l a t i o n a t 4 - a r y l o f 1 , 4 - d i su b s t i t u t e d 1 , 2 , 3 - t r i a -
z o le s Tetrahedron 76 1 3 0 9 8 5 ; ( d ) Z h a o F , L i u Y , Y a n g
S , X i e K a n d J i a n g Y 2 0 1 7 P d - c a t a l y z e d s e l e c t i v e N ( 3 ) -
o r t h o C - H a r y l a t i o n o f 1 , 4 - d i s u b s t i t u t e d 1 , 2 , 3 - t r i a z o le s
Org. Chem. Front. 4 1 1 1 2 ; ( e ) G o n z a l e z - M o j i c a N ,
A l m az a n- S a n c h e z L , G a rc i a - T o r r e s J , e t a l. 2 0 1 9
O x i d at i o n o f 1 , 4 - d i s u b s t i t u t e d - 1 , 2 , 3 - t r i a z o l e s w i t h
H O - C F C O H : e f fi c i e n t s y n t h e s i s o f 1 , 2 , 3 - t r i a z o le
V 2 0 1 0 T r a n s it i o n - m e t a l - f r e e c a t a l y t i c s y n t h e si s o f 1 ,5 -
d i a r y l- 1 , 2 ,3 - t r i a z o l e s Org. Lett. 12 4 2 1 7 ; ( b ) C he n g X ,
L i u W a n d H u a n g Z 2 0 1 3 S o d i u m h y d r i d e - m e d i at e d
s y n t h e si s o f 1 , 5 - d ia r y l - 1 ,2 , 3 - t r i a z o l e s f r o m a n t i- 3 - ar y l-
2 , 3 - d ib r o m o p r o p a n o i c a c i d s a n d o r g a n i c a z i d e s Chin.
Chem. Lett. 24 7 6 4 ; ( c ) M a i u o l o L , R u s s o B , A l gi e r i V ,
e t a l . 2 0 1 9 R e g i o s e l e c t i v e s y n t h e s i s o f 1 , 5 - d is u b s t i t u t ed
1 , 2 , 3 - t r i a z o l e s b y 1 , 3 - d ip o l a r c y c lo a d d i t io n : R o l e o f
E r ( O T f ) , i o n i c l iq u i d a n d w a t e r Tetrahedron Lett. 60
3
2
2
3
2
3 - o x i d es Synth. Commun. 49 6 7 9 ; ( f) M a X , L i H , X i n
H , D u W , A n d e r s o n E , D o n g X a n d J i a n g Y 2 0 2 0 1 3 . ( a ) G o n z a l e z - Ca l d e r o n D , S a n t i ll a n - I n i e s t a I , G o n za l e z-
6
7
2
C o p pe r - c at al yz e d i n t r a m o l e c u l a r C - H a l k o x y l a t io n o f
d i ar y lt r i az o l es : S y n t h e s i s o f t r i c y c l i c t r i a z o l e b e n z o x -
a zi n es Org. Lett. 22 5 3 2 0 ; ( g ) W a n g J , Y a n g J , F u X ,
Q i n G , X i a o T a n d J i a n g Y 2 0 1 9 S y n t h e s i s o f t r i a z o l e -
f u s e d p h en an t h r i d i n e s t h r o u g h P d - c a t a l y z e d i n t r a m o l e c -
u l ar p h e n yl C - H a c t i v a t i o n o f 1 , 5 - d i a r y l - 1 , 2 , 3 - tr ia z o le s
Synlett 30 1 4 5 2
G o n z a l e z C , et al. 2 0 1 5 A n o v e l a n d f a c il e s y n t h es i s o f
1 , 4 , 5 - t r i s u b s t it u t e d 1 , 2 , 3 - t r i a z o le s f r o m b e n z y l i c a lc o -
h o l s t h r o u g h a o n e - p o t , t h r e e - c o m p o n e n t s y s t e m Tetra-
hedron Lett. 56 5 1 4 ; ( b ) G u o N , L i u X , X u H , et al.
2 0 1 9 A s i m p l e r o u t e t o w a r d s t h e s y n t h e s i s o f 1 ,4 , 5-
t r i s u b s t it u t e d 1 , 2 , 3 - t r i a z o l e s f r o m p r im a r y a m i n e s a nd
1 , 3 - d ic a r b o n y l c o m p o u n d s u n d e r m e t a l - f r e e c o n di t i o ns
Org. Biomol. Chem. 17 6 1 4 8 ; ( c ) C h e n Z , Y a n Q , L iu Z ,
X u Y a n d Z h a n g Y 2 0 1 3 C o p p e r - m e d i a t e d s y n t h es i s o f
1 , 2 , 3 - t r i a z o l e s f r o m N - to s y lh y d r a z o n e s a n d a ni l i ne s
Angew. Chem. Int. Ed. 52 1 3 3 2 4 ; ( d ) C h e n Z , L iu Z ,
C a o G , e t a l . 2 0 1 7 R e c e n t a d v a n c e s i n m u l t ic o m p on en t
s y n t h e si s o f 1 , 4 , 5 - t r i s u b s t it u t e d 1 , 2 , 3 - t r i a z o l e s Adv.
Synth. Catal. 359 2 0 2
5 . ( a ) R o h r i g U , M a j j i g a p u S , G r o s d i d i e r A , e t a l . 2 0 1 2
R at i o n a l d e si g n o f 4 - a r y l - 1 , 2 , 3 -t ri a z o l e s f o r i n d o l e a -
m i n e 2 , 3 - d io x y g e n a s e 1 i n h i b i t i o n J. Med. Chem. 55
5 2 7 0 ; ( b ) R o h r i g U , R e y n a u d A , M a j j i g a p u S , e t a l .
2 0 1 9 I n h i b i ti o n m e c h a n i s m s o f i n d o l e a m i n e 2 , 3 - d io x y -
g e na s e 1 ( I D O 1 ) J. Med. Chem. 62 8 7 8 4
6 . ( a ) T o t i r M , P a d a y a t t i P , H e l f a n d M , e t a l . 2 0 0 6 E f f e c t
o
f
t
h
e
i
n
h
i
b
i
t
o
r
-
r
e
s
i
s
t
a
n
t
M
6
9
V
s
u
b
s
t
i
t
u
t
i
o
n
o
n
t
h
e
1
4
.
W
u
L
,
X
i
e
Y
,
C
h
e
n
Z
,
N
i
u
Y
a
n
d
L
i
a
n
g
Y
2
0
0
9
A
s t r u c t ur e s a n d p o p u l a t i o n s o f t r a n s - e n a m i n e b- l a c t a m a s e
i n t er m e d i at e s Biochemistry 45 1 1 8 9 5 ; ( b ) Z h a n g B 2 0 1 9
C o m pr e h en s i ve r e v i e w o n t h e a n t i -b a c t e r i a l a c ti v i t y o f
c o n v e n i e n t s y n t h e s i s o f 1 - s u b s t it u t e d 1 , 2 , 3 - t r i a z o le s v ia
C u I / E t N c a t a l y z e d ‘ c l i c k c h e m is t r y ’ f r o m a z i d es a nd
a c e t y l e n e g a s Synlett 1 4 5 3
3
1
,
2
,
3
-
t
r
i
a
z
o
l
e
h
y
b
r
i
d
s
E
u
r
.
J
.
M
e
d
.
C
h
e
m
.
1
6
8
3
5
7
;
1
5
.
(
a
)
A
n
d
e
r
s
e
n
J
,
B
o
l
v
i
g
S
a
n
d
L
i
a
n
g
X
2
0
0
5
E
f
fi
c
i
e
n
t
( c ) F e r M , L e C o r re L , P i e t r a n c o s t a N , e t a l . 2 0 1 8
B ac t e r i a l t r a n s f e r a s e M r a Y , a s o u rc e o f i n s p i r a t i o n
t o w a r d s n ew a n t i b i o t i c s Curr. Med. Chem. 25 6 0 1 3
7 . ( a ) B i an J , Z h a n g L , H a n Y , W a n g C a n d Z h a n g L 2 0 1 5
H i s t o n e d ea c et y l a s e i n h i b i t o r s : P o t e n t a n t i -l e u k e m i c
a ge n t s Curr. Med. Chem. 22 2 0 6 5 ; ( b ) K a l i n i n D , J a n a
S , P f af e n r o t M , e t a l . 2 0 2 0 S t r u c t u r e - b a s e d d e s i g n ,
s y n t he s i s , a n d b i o l o g i c a l e v a l u a t i o n o f t r i a z o le - b a s e d
s m H D A C 8 i n h i b i t o r s ChemMedChem 15 5 7 1
o n e - p o t s y n t h e s i s o f 1 - a r y l 1 , 2 , 3 - t r i a z o le s f r o m a ry l
h a l i d e s a n d t e r m i n a l a l k y n e s i n t h e p r e s e n c e o f s o d i um
a z i d e Synlett 2 9 4 1 ; ( b ) C h a n D , L a u g h t o n C , Q u e e ne r S
a n d S t e v e n s M 2 0 0 2 S t r u c t u r a l s t u d i e s o n b io a ct i v e
c o m p o u n d s . P a r t 3 6 : D e s i g n , s y n t h e s i s a n d b i o lo g i c al
e v a lu a t i o n o f p y r im e th a m i n e - b a s e d a n t i f o l a t e s a ga i n s t
p n e u m o c y s t is c a r in ii Bioorg. Med. Chem. 10, 3 00 1;
( c ) F l e tc h e r J , W a l z S a n d K e e n e y M 2 0 0 8 M o no s u b-
s t it u t e d 1 , 2 ,3 - t r i a z o l e s f r o m t w o - s te p o n e - p o t d ep ro t ec -
8 . ( a ) E l A k r i K , B o u g r i n K , B a l z a ri n i J , F a r aj A a n d
B en h i d a R 2 0 0 7 E f fi c i e n t s y n t h e s i s a n d i n v i t r o c y t o -
s t at i c a ct i v it y o f 4 - s u b s t i t u t e d t r i a z o l y l -n u c l e o s i d e s
Bioorg. Med. Chem. Lett. 17 6 6 5 6 ; ( b ) B o n a n d i E ,
t io n / c li c k
a d d it i o n s
o
f
t
r
i
m
e
t
h
y
l
s
i
l
y
l
a
c
e
t
y
l
e
n
e
Tetrahedron Lett. 49 7 0 3 0 ; ( d ) J i a n g Y , K u a n g C a nd
Y a n g Q 2 0 1 1 F a c i l e a n d q u i c k s y n t h e s i s o f 1 - m o no -
s u b s t i tu t e d a r y l 1 , 2 , 3 - t r i a z o l e s : a c o p p e r - f r e e [ 3 ?2 ]

J. Chem. Sci.
( 2 0 2 0 ) 1 3 2 : 1 5 4
P
a
g
e
7
o
f
7
1 5 4
c yc l o a d d i t i o n Tetrahedron 67 2 8 9 ; ( e ) J i a n g Y , K u a n g
C a n d Y a n g Q 2 0 0 9 T h e u s e o f c a l c i u m c a rb i d e i n t h e
s y n th e s i s o f 1 - m o n o s u b s t i t u t e d a r y l 1 , 2 , 3 - t r i a z o le v i a
c li c k c h em i s t ry Synlett 3 1 6 3 ; ( f) G i e l M , S m ed le y C ,
M ac k i e E , G u o T , et al. 2 0 2 0 M e t a l - fr e e s y n t h e s i s o f
f u n c ti o n al 1 - s u b s t i t u t e d -1 , 2 , 3 - t r i a z o l e s f ro m e t h e n e s u l -
f o n y l fl u o r i d e a n d o r g a n i c a z i d e s Angew. Chem. Int. Ed.
59 1 1 8 1 ; ( g ) S h a n g J , F u H , L i Y , Y a n g T , G a o C a n d L i
Y 2 0 1 9 C o p p e r -c a t a l y z e d d e c a r b o x y l a t i o n / c y c l o a d d i -
t i o n c as c ad e o f a l k y n y l c a rb o x y l i c a c i d s w i t h a z i d e
Tetrahedron 75 2 5 3 ; ( h ) H a n C , D o n g S , Z h a n g W a n d
C h en Z 2 0 1 8 O n e - P o t S y n t h e s i s o f 1 - m o n o s u b s t i t u t e d
1 , 2 , 3 - t r ia z o l es f ro m p r o p a r g y l a l c o h o l Synlett 29 6 7 3 ;
( i ) L i u Y , H a n C , M a X , Y a n g J , F e n g X a n d J i a n g Y
2 0 1 8 O n e - p o t s y n t h e s i s o f 1 - m o n o s u b s t i t u t e d - 1 , 2 ,3 -
t r i a zo l e s f r o m 2 - m e t h y l - 3 -b u t y n - 2 -o l Tetrahedron Lett.
59 6 5 0 ; ( j ) W u L , Y a n B , Y a n g G a n d C h e n Y 2 0 1 3
G r ee n s y n t he s i s o f 1 - m o n o s u b s t i t u t e d 1 , 2 , 3 -t r i a z o le s v i a
‘ c l i ck c h em i s t r y ’ i n w a t e r Heterocycl. Commun. 19 3 9 7 ;
( k ) H a e bi c h D , B a r t h W a n d R o e s n e r M 1 9 8 9 S y n t h e s i s
o f 3 ’ - ( 1 , 2, 3 - t r i a z o l - 1 - y l ) -3 ’ - d e o x y t h y m i d i n e s Heterocy-
c a r b o n - 1 3 n u c l e a r m a g n e t i c r e s o n a n c e s p e c t r a o f 1 -( 1 -
a d a m a n t y l ) -D2 - 1 ,2 ,3 - t r i a z o li n e s a n d - 1 H - 1 ,2 , 3 - t r i a z ol e s
J. Org. Chem. 46 1 8 0 0 ; ( n ) H u a n g Z , W a n g R , S h en g S ,
Z h o u R a n d C a i M 2 0 1 3 P r e p a r a t i o n o f p o l y s t y r e ne -
s u p p o r t e d v i n y l s u l f o n e a n d i ts a p p l i c a t io n i n t he s o l i d-
p h a s e o r g a n i c s y n t h e s i s o f 1 - m o n o s u b s t i tu te d 1 ,2 , 3-
t r i a z o l e s React. Funct. Polym. 73 2 2 4 ; ( o ) N a ud J ,
L e m k e C , G o u d r e a u N , B e a u l i e u E a n d W h it e P 2 00 8
P o t e n t t r i a z o l y l - p r o l i n e - b a s e d i n h i b i t o r s o f H C V N S 3
p r o t e a s e Bioorg. Med. Chem. Lett. 18 3 4 0 0 ; ( p ) Y an g Q ,
J i a n g Y a n d K u a n g C 2 0 1 2 F a c i l e o n e - p o t s y n t he s i s o f
m o n o s u b s t i tu te d 1 - a r y l - 1 H - 1 , 2 , 3 - t r i a z o l e s f r o m a ry l -
b o r o n i c a c i d s a n d p r o p - 2 - y n o i c A c i d ( = p r o p i o l ic a ci d )
o r c a l c i u m a c e t y l i d e ( = c a l c i u m c a r b i d e ) a s a ce t yl e ne
s o u r c e Helv. Chim. Acta 95 4 4 8 ; ( q ) X u M , K ua n g C ,
W a n g Z , Y a n g Q a n d J i a n g Y 2 0 1 1 A n o v e l a p p ro a ch t o
1 - m o n o s u b s t i t u t e d 1 , 2 , 3 - t r i a z o le s b y a c l i c k c y c l oa dd i -
t io n / d e c a r b o x y l a ti o n p r o c e s s Synthesis 2 2 3 ; ( r) K o -
l a r o v ic A , S c h n u r c h M a n d M i h o v il o v i c M 2 01 1
T a n d e m c a t a l y s i s : F r o m a l k y n o i c a c i d s a n d a r y l i od i d es
t o 1 , 2 , 3 - t r i a z o le s i n o n e p o t J. Org. Chem. 76 2 6 1 3
cles 29 2 0 8 3 ; ( l ) K a d a b a P 1 9 9 2 T r i a z o l i n e s . 2 5 . 1 , 3 - 1 6 . ( a ) Y a n g H , L i Y , J i a n g M , W a n g J a n d F u H 2 01 1
C y cl o a d d i t i on o f a r y l a z i d e s t o e n a m i d e s a n d t h e
s y n th e s i s o f 1 - a ry l - 5 -a m i d o - 1 , 2 , 3 - t r i a z o l i n e s J. Org.
Chem. 57 3 0 7 5 ; ( m ) S a s a k i T , E g u c h i S , Y a m a g u c h i M
a n d E s a k i T 1 9 8 1 S y n t h e s i s o f a d a m a n t a n e d e r iv a t i v e s .
5 2 . 1 , 3 - D i po l a r c y c l o a d d i t i o n r e a c t i o n s o f 1 - a z i -
d o ad am an t an e . R e a c t i v i t y , r e g i o s e l e c t i v i t y , a n d
G e n e r a l c o p p e r - c a t a l y z e d t r a n s f o r m a t i o n s o f f u n ct i o na l
g r o u p s f r o m a r y lb o r o n i c a c i d s i n w a t e r Chem. Eur. J. 17
5 6 5 2 ; ( b ) T a o C , C u i X , L i J , L i u A , L i u L a n d G u o Q
2 0 0 7 C o p p e r - c a t a l y z e d s y n t h e si s o f a r y l a z i d es a nd
1 - a r y l - 1 ,2 , 3 - t r i a z o l e s f r o m b o r o n i c a c i d s Tetrahedron
Lett. 48 3 5 2 5