Methanesulfonic anhydride-promoted sustainable synthesis of thioesters from feedstock acids and thiols

Article abstract of DOI:10.1007/s12039-020-01871-5

Abstract: An unprecedented metal-, halogen- and solvent-free, MSAA-promoted S-carbonylation of thiols with feedstock acids has been developed. This new transformation provides an efficient and atom-economic strategy for the synthesis of thioesters in a single operation from readily available and inexpensive starting materials. The reaction avoids the use of expensive and hazardous coupling reagents, bases and generates water as the only by-product, thus making this chemical synthetic process more viable, environment-friendly and contributing towards sustainable chemistry. Graphic abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s12039-020-01871-5

J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 : 2 0
Ó I n d ia n A c a d e m y o f S c i en c es
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REGULAR ARTICLE
Methanesulfonic anhydride-promoted sustainable synthesis
of thioesters from feedstock acids and thiols
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P A LL A V I S I N G H a n d R A M A K R IS H N A P E D D I N T I
D e p ar t m e n t o f C h e m i s t ry , I n d i a n I n s ti t u t e o f T e c h n o l o g y R o o r k e e , R o o r k e e , U t t a r a k h a n d 2 4 7 6 6 7 , I nd i a
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Abstract. A n u n p r e c e d e n t e d m e t a l - , h a l o g e n - a n d s o l v e n t - f r e e , M S A A - p r o m o t e d S- c a r b o n y l a t i o n o f t hi o l s
w i t h f e e d s t o c k a c i d s h a s b e e n d e v e l o p e d . T h i s n e w t r a n s f o r m a t i o n p r o v i d e s a n e f fi c i e n t a n d a t o m - e c o n o m i c
s t r a t eg y f o r t h e s y n t h e s i s o f t h i o e s t e r s i n a s i n g l e o p e r a t io n f r o m r e a d i ly a v a il a b l e a n d i n e x p e n s i v e s t a r ti n g
m at e r i a l s . T h e r e a c t i o n a v o i d s t h e u s e o f e x p e n s i v e a n d h a z a r d o u s c o u p l in g r e a g e n t s , b a s e s a n d g e ne r a te s
w a t er a s t h e o n l y b y - p r o d u c t , t h u s m a k i n g t h i s c h e m i c a l s y n t h e ti c p r o c e s s m o r e v i a b l e , e n v ir o n m e n t - f r ie n dl y
a n d c o n t r i b u t i n g t o w a r d s s u s t a i n a b l e c h e m is t r y .
Keywords. D e h y d r a t i v e t h i o e s t e r i fi c a t i o n ; S- c a r b o n y l a t i o n ; M S A ; M S A A ; M i x e d a n h y d r i d e .
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Electronic supplementary material: The online version of this article (https://doi.org/10.1007/s12039-020-01871-5) contains
supplementary material, which is available to authorized users.

2 0 P a g e 2 o f 1 2
J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 : 2 0
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3. Results and Discussion
r
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Table 1. O p t i m i 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 .
R e a g e n t
( e q u i v )
S o l v e n t
( m L )
b
Y i e l d ( % )
E
n
t
r
y
T e m p e r a t u r e
8 0 °C
T
i
m
e
(
h
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1
2
3
T F AA ( 1 . 3 )
T F AA ( 1 . 3 )
T F AA ( 1 . 3 )
M e C N
( 5 )
6
6
9 0
9 0
2 5
C H C l
2
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e
fl
u
x
2
( 5 )
T H F
( 5 )
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fl
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x
1
2
c
4
T F A A ( 1 . 3 )
M S A A ( 1 . 3 )
M S A A ( 1 . 3
N e a t
C H C l ( 5 )
8 0 °C
8 0 °C
R e fl u x
2 4
4
4
N D
9 6
9 6
5
6
2
2
M e C N
( 5 )
7
8
9
1 0
1 1
1 2
M S A A ( 1 . 3 )
M S A A ( 1 . 2 )
M S A A ( 1 . 0 )
M S A A ( 1 . 3 )
M S A A ( 1 . 3 )
M S A A ( 1 . 3 )
–
N e a t
N e a t
N e a t
N e a t
N e a t
N e a t
–
8 0 °C
8 0 °C
8 0 °C
6 0 °C
4 0 °C
1 0 0 °C
8 0 °C
4
6
1 5
8
1 5
4
2 4
9 6
9 0
8 5
8 5
8 5
9 6
N R
d
1
3
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C
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s
:
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d
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d
N
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=
N
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r
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a
c
t
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n
.

J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 : 2 0
P a g e 7 o f 1 2 2 0
Table 2. M S A A -p ro m o t e d S- c a r b o n y l a t i o n o f a r y l t h i o l s w i t h
c a rb o x y l i c a c i d s .
a
b
a
R e a c t i o n c o n d i t i o n s : f e e d s t o c k a c i d 1 ( 0 .5 m m o l ) , a l r y l t h i o l 2
( 0 . 6 m m o l ) , M S A A ( 0 . 6 5 m m o l ) , 8 0 °C , 4 h .
Y i e l d o f p u r e p r o d u c t .
b
t
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J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 : 2 0
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Table 3. M S A A - p ro m o t e d S -c a r b o n y l a t i o n o f a l k y lt h i o l s
w it h c ar b o x y l i c a ci d s .
a
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Scheme 2. G r a m - s c a le s y n t h e s i s o f t h i o e s t e r 3af.

2
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J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 : 2 0
1 4 . A z u m a H , O k a n o K a n d T o k u y a m a H 2 0 1 1 S y n t he s i s o f
a c y ls i l a n e s b y p a l l a d i u m - c a t a l y z e d c r o s s - c o u p li n g r ea c-
t io n o f t h i o l e s t e r s a n d s i ly l z i n c c h l o r i d e s Chem. Lett. 40
9 5 9
p
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1 5 . K o ts u k i H , Y o s h i m u r a N , U s h io Y , O h ts u k a T a n d O c h i
M 1 9 8 6 F a c i l e r e d u c t io n o f b e n z e n e t h i o l e s t e r s u nd er
m i ld c o n d i t io n s w i t h z i n c b o r o h y d r id e Chem. Lett. 15
1 0 0 3
1 6 . F u k u y a m a T , L i n S C a n d L i L 1 9 9 0 F a c i l e r e d u c t i on o f
e t h y l t h i o l e s t e r s t o a l d e h y d e s : a p p l i c a t io n t o a t ot a l
s y n t h e s i s o f ( ?) - n e o t h r a m y c i n A m e t h y l e t h e r J. Am.
Chem. Soc. 112 7 0 5 0
Supplementary Information (SI)
C o p ie s o f N M R s p e c t r a o f t h e p r o d u c t s a r e a v a i la b l e i n
S u p p l e m en t a r y I n f o r m a t i o n .
Acknowledgements
P
.
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t
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.
1 7 . N a g a s h i m a E , S u z u k i K a n d S e k i y a M 1 9 8 3 R ea c t i on s
o f 2 , 2 - d ic h l o r o v i n y l a n d 2 , 2 - d i c h l o r o v i n y l i d e n e s u l fi d e s
w i t h b u t y l l i th iu m Chem. Pharm. Bull. 31 3 3 0 6
1 8 . Y o u s if N M , P e d e r s e n U , Y d e B a n d L a w e s s on S O
1 9 8 4 S t u d i e s o n o r g a n o p h o s p h o r u s c o m p ou nd s .
X L V I I I . S y n t h e si s o f d i t h i o e s t e r s f r o m p h o s ph o r us -
a n d s u l f u r - c o n t a i n i n g r e a g e n t s a n d c a r b o x y li c a ci d s a nd
t h e i r d e r iv a t i v e s Tetrahedron 40 2 6 6 3
References
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S t u d i e s o n t h e c a t a l y t i c o x i d a t i o n o f a l k a n e s a n d a l k e n e s
b y t i ta n i u m s i li c a t e s J. Catal. 149 1 9 5
2 . A n d r a d e C K Z a n d A l v e s L M 2 0 0 5 E n v i r o n m e n t a l l y
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L i e b es k i n d L S 2 0 0 7 A m b i e n t t e m p e r a t u r e s y n t h e si s o f
h i g h e n an t io p u r i t y N -p ro t e c t e d p e p t i d y l k e t o n e s b y
p ep ti d y l t h i o l e s t e r - b o r o n i c a c i d c r o s s - c o u p l i n g J. Am.
Chem. Soc. 129 1 1 3 2
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s y n th e s i s o f p e p t i d e s f ro m t h i o a c i d s a n d a m i n e s w i t h t h e
S a n g er a nd M u k a i y a m a r e a g e n t s Angew. Chem. Int. Ed.
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P 2 0 1 1 S y n t h es i s o f d i a r y l k e t o n e s via a p h o s p h in e - f r e e
F u k u y a m a r e ac t i o n Chem. Commun. 47 1 2 6 7 9
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49 3 6 3 3
K u ma r A a n d S a k h u j a R 2 0 1 5 I m i d a z o l i u m - s u p po r te d
b e n z o t r i a z o l e : a n e f fi c i e n t a n d r e c o v e r a b l e a c t i va t i ng
r e a g e n t f o r a m i d e , e s t e r a n d t h i o e s t e r b o n d f o r m a t i o n i n
w a t e r RSC Adv. 5 8 2 1 9 9
6 3 . S i n g h P , S i n g h U P a n d P e d d i n t i R K 2 0 1 7 P T S A -
c at al yz e d f u n c ti o n a l i z a t i o n o f h y d r o q u i n o n e s w i t h b e n -
z h yd r y l a lc o h o l s i n w a t e r Tetrahedron Lett. 58 2 8 1 3
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t r a n s f e r – a r o m a t i z a t i o n – a l k y l a t i o n d o m i n o a p p r o a c h :
f a ci l e s y n t h e si s o f b r a n c h e d h y d r o q u i n o n e s f r o m p-
q u i n o l s a n d d i ar y l c a rb i n o l s ChemistrySelect 2 3 6 2 2
W a n g H 2 0 1 5 C a t a l y s t- f r e e d i r e c t d e c a r b o x y l at i v e
c o u p l in g o f a- k e to a c i d s w i t h t h i o l s : A f a c il e a cc es s
t o t h i o e s t e r s Org. Biomol. Chem. 13 7 3 2 3
6 5 . S i n g h P a n d P e d d i n t i R K 2 0 1 7 H a r n e s s i n g t h e c a t a l y t ic 7 5 . P i j p e r T C , R o b e r t u s J , B r o w n e W R a n d F e r i n g a B
b e ha v i o ur o f 1 , 1 , 1 , 3 , 3 , 3 - h e x a fl u o r o - 2 - p r o p a n o l ( H F I P ) :
A n e x pe d i t i o u s s y n t h e s i s o f t h i o e s t e rs Tetrahedron Lett.
58 1 8 7 5
L 2 0 1 5 M i l d T i - m e d i a t e d t r a n s f o r m a t i o n o f t- b u t y l
t h i o - e t h e r s i n t o t h i o - a c e t a t e s Org. Biomol. Chem. 13
2 6 5
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c a t io n of a l d e h y d e s w i t h d i s u l fi d e s vi a N H C - c a t a l y z e d b u l k y p y r id in e a s a n e f fi c ie n t r e u s a b l e h o m o g e ne o u s
c a r bo ny l u m po l u ng s t r a t e g y Tetrahedron Lett. 53 5 13 6 c a t a l y s t RSC Adv. 3 1 5 3 2 7
6 7 . D a n W , D e n g H , C h e n J , D i n g J a n d W u H 2 0 1 0 A n e w 7 7 . K a t r i t z k y A R , S h e s t o p a l o v A A a n d S u z u k i K 2 00 4 A
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n e w c o n v e n i e n t p r e p a r a t i o n o f t h i o l e s t e r s u t i li z i n g N-
a c y lb e n z o t r i a z o le s Synthesis 11 1 8 0 6
6 8 . F e n g J , L v M - F, L u G -P a n d C a i C 2 0 1 5 D i r e c t 7 8 . U n o T , I n o k u m a T a n d T a k e m o t o Y 2 0 1 2 N H C -
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o x i d at i ve c o up l i n g o f t h i o l s a n d b e n z y l i c e t h e r s v i a
C ( s p ) – H a ct i v a t i o n a n d C – O c l e a v a g e t o l e a d t h i o e s t e r s
c a t a l y z e d t h i o e s t e r i fi c a t i o n o f a l d e h y d e s b y e xt e rn al
r e d o x a c t i v a t io n Chem. Commun. 48 1 9 0 1
3
Org. Biomol. Chem. 13 6 7 7
6 9 . R o ng G , M ao J , L i u D , Y a n H , Z h e n g Y a n d C h e n J
7 9 . I r a n p o o r N , F i r o u z a b a d i H , K h a l il i D a n d M o t e va l l i S
2 0 0 8 E a s i l y p r e p a r e d a z o p y r i d i n e s a s p o t e n t a nd
r e c y c l a b l e r e a g e n t s f o r f a c il e e s t e r i fi c a t i o n r e a ct i o ns .
A n e f fi c i e n t m o d i fi e d m i t s u n o b u r e a c ti o n J. Org. Chem.
73 4 8 8 2
2
2 0 1 5 F o r m a t io n o f C ( s p ) – S b o n d s t h r o u g h d e c a r b o x y -
l at i o n o f a- o x o c a r b o x y l i c a c i d s w i t h d i s u l fi d e s o r
t h i o ph en o l s RSC Adv. 5 2 6 4 6 1
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t h i o es t e r i fi c at i o n o f a l d e h y d e s a n d a l c o h o l s Adv. Synth.
Catal. 355 3 5 5 8
i fi c a t io n s f r e e o f a c t i v a t in g a g e n t a n d t h i o l : A t hr e e-
c o m p o n e n t r e a c t io n o f c a r b o x y li c a c i d s , t h i o u r e a s , a nd
m i c h a e l a c c e p t o r s Adv. Synth. Catal. 357 2 6 4 4
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T h i o e st e r i fi c a ti o n o f a l k y l b e n z e n e s w i t h t h i o l s v i a
c o pp er - c a ta l y z e d c r o s s - d e h y d r o g e n a t i v e c o u p l i n g w i t h -
o u t a d i r e ct i n g g r o u p Adv. Synth. Catal. 356 3 0 9 9
7 2 . H e C , Q i a n X a n d S u n P 2 0 1 4 S y n t h e s e s o f t h i o l a n d
s el e n o l e st e r s b y o x i d a t i v e c o u p l i n g r e a c t i o n o f a l d e h y -
d e s w i t h R Y Y R ( Y = S , S e ) u n d e r m e t a l - fr e e c o n d i ti o n s
Org. Biomol. Chem. 12 6 0 7 2
S - a r y l t h i o a c e t a t e s f r o m a r y l h a l i d e s a n d p o t as s i u m
t h i o a c e t a t e Tetrahedron Lett. 48 3 0 3 3
8 2 . P e t r i ll o G , N o v i M , G a r b a r i n o G a n d F i l i b e r t i M 1 98 9
T h e r e a c ti o n b e t w e e n a r e n e d i a z o n iu m t e t r a fl u o r o b o ra t es
a n d a l k a l i n e t h i o c a r b o x y l a t e s i n D M S O : A c o n v en i en t
a c c e ss t o a r y l t h i o l e s t e r s a n d o t h e r a r o m a ti c s u l f ur
d e r iv a ti v e s Tetrahedron 45 7 4 1 1