Conceptual approach to the synthesis of symmetrical 1,3-diynes from β-bromo vinyl carboxylic acids

Article abstract of DOI:10.1007/s12039-019-1693-7

Abstract: A conceptual route has been developed for the synthesis of 1,3-diyne from β-bromo vinyl carboxylic acids. The reaction of the β-bromo vinyl carboxylic acid with palladium catalyst is conceptually similar to the decomposition of 2-diazoniumbenzoic acid to benzyne. In the presence of palladium catalyst, the β-bromo vinyl carboxylic acid undergoes a fragmentation to generate terminal alkyne. The terminal alkyne undergoes dimerisation in the presence of palladium catalysts to produce the product 1,3-diyne. Graphic abstract: A conceptual route has been developed for the synthesis of 1,3-diyne from β-bromo vinyl carboxylic acids. To the best of our knowledge, we are the first ones reporting the synthesis of 1,3-diyne in a catalytic way without the requirement of any prefunctionalized alkyne unit(s).[Figure not available: see fulltext.]

Full text of DOI:10.1007/s12039-019-1693-7

J. Chem. Sci. (2 0 2 0 ) 1 32 :4
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RAPID COMMUNICATION
Conceptual approach to the synthesis of symmetrical 1,3-diynes
from b-bromo vinyl carboxylic acids
RA J U SI NGHA
De p ar t m en t of Ch e m is t ry , P an s ku r a B anam al i C ol leg e (A ut onom o us ) , P ans ku r a R .S . ,
Pu r b a Me di ni pu r 72 1 15 2, W es t Be n gal , In di a
E- ma i l: r aj us i ng ha7 0@ gm ai l.c om
MS r ecei v ed 6 J u ne 2 01 9 ; r ev i s ed 1 A u gu s t 2 0 1 9; accep t ed 8 A u g u st 2 0 1 9
Abstract. A co nc e pt ua l r ou te ha s bee n dev elo ped fo r t he s ynt hes i s of 1, 3-d iy ne fr om b-b ro m o vi n yl c ar -
b o x y l ic ac i ds . Th e r eac ti on of th e b-b ro m o v i nyl car boxy l ic aci d wi t h pal l adi um cat al ys t i s con cep t u a l l y
s i mi l ar to th e de co m po s it io n of 2- d ia zon i um ben z oi c aci d t o ben zyn e. In t he pr es enc e of pal l adi um c at a l y st ,
t h e b- br o m o vi ny l ca rb ox yl ic ac i d u nder goe s a fr agm ent a t io n t o g ene rat e t erm i nal al kyn e. The t er m i n al
a lk y n e un de r go es di m er is a ti on in th e pr es ence of pal l adi um cat al ys t s t o pr oduce t he pr oduc t 1, 3-d iyn e .
Keywords. b- br om o vi ny l ca rb ox yli c aci d; pal l adi um ; ben zyne; t erm i nal al kyn e; 1, 3-d iy ne .
1
2
1
. Introduction
na nop ar t ic le s. Hua ng a nd c o- wor ke r s ha ve re por t ed
th e syn the si s of 1,3 -d iyne s via c o pp e r-c a ta l yz e d
de c ar bo xyl at ive c oupl ing of sub sti tut ed pota s s ium
1
, 3 - Diy n e s a re a n i mpo r ta nt cl a ss of o rg ani c b uil din g
1
3
b l o ck s a n d th e y f ou nd ap pl i ca ti o ns i n o rg an ic syn -
t h e si s , ma t e ria ls sc i enc e as wel l as i n p har ma c eutic a l
pr op iola te s wit h 1,1 -d ibr om o- 1-a lke ne s. The lit er a -
tu re r ep or ts r es olv e th at th e 1,3 -d iyne synt he sis
in volv es th e r eq uir e me nt of e ith er one or two te rm ina l
a lky ne s. He r ei n, we a re r ep or tin g a c onc e ptua l
a ppr oa c h to th e syn the si s of 1,3 -d iyne s f r om b- br omo
vi nyl c ar bo xyl ic a ci ds. To th e be st of ou r kno wle dge ,
we a re th e fi rs t on es r ep or tin g th e syn the si s of 1,3-
di yne in a c at al yti c wa y wit hout th e r eq uir e m e nt of
a ny pr e f unc tio na liz e d a lky ne un it( s) .
1
s c i en c e . 1 , 3- Diy ne s se rv e as t he i mpo r ta nt sc a ff ol d to
2
t h e s y n th e s is o f di f fe re nt n at ur al p ro du ct s, or ga ni c
3
c o n d u c to rs , s u p r amo le cu la r swi t ch es , ma cr oc yc li c
4
5
6
a n n u le n e s a n d v a ri o us el e ct ro n- ri c h ma te ri a ls. C on-
s i d er in g th e i r im po r ta nce , t re men do us ef f or t ha s be e n
t a ke n fo r th e d e v el o pme nt o f ef fic ie nt an d co s t- e ff e c -
t i v e me t h o d o lo g y i n r ece nt y ear s.
Th e d im e ris a ti on of t er mi na l al k yn es ar e t h e c la s-
s i c al a p p ro a c h to t he sy nt h es is of 1 ,3- di yn e s a nd
7
8
9
Gl as e r c o u p li n g , Hay co up l in g an d Eg l in t o n c ou- 2. Experimental
1
0
p l i n g a re th e p i on ee ri ng wo rk i n t hi s fie ld. The se
c o up l in g re a c ti o ns i nv ol ve co pp er -c at a ly ze d di me r i-
s a t io n o f te rm in a l al k yn es wh er e t he me ta l or a er i al
o x yg en a c ts a s th e ox i da nt . Re cen t ly , v ari o us gr ou ps
h a ve d e v e lo p e d ef fic ie nt di me ri s at io n me th odo log ie s
i n th e p re s e n c e o r ab se nc e of me ta l ca t al ys ts. W a ng
et al. , h a v e re p o rt ed t he sy nt h es is of 1, 3- di yne s via
c ro s s -c o u p li n g o f t er mi na l al k yn es wi th 1- br o-
The di azo coup l in g rea c t io n of 2- am i nob enz oi c a ci d i s a
cl as s i cal app roach fo r t he s ynt hes i s of b en zy n e
1
S ch e m e 1 ). R ecent l y Ki m et al. , hav e rep or te d t ha t
4
(
2
- brom o ben zoi c aci d pr oduc es ben zyn e i n pr ese n ce o f
1 5
pal l adi um cat al ys t . Ho w eve r, i n bot h t he cas e , t he in situ
gen erat ed ben zyn e und er go [2 ?2 ?2] cyc lo addi t io n t o f or m
t ri phe nyl en e (S ch em e 1 ).
We env i s i oned t hat t he rea c t io n of b-b rom o vi n yl c ar -
11
m o al k y n e in th e pr es en ce o f Cu I ca t al ys t. The c ro ss- box yl i c aci ds wi t h pal l adi um cat al ys t wi l l pr oduc e a si m i l ar
c o u p li n g o f a lk y n y l br o mid e wi th al k yn yl b or oni c a ci d i nt erm ed i at e pal l adi um com pl ex, wh ich wi l l und er g o a
a l so p ro d u c e s 1 ,3 -d iy ne s i n t he pr es en ce of C uF e O
2
rea rra nge m ent t o fo rm t erm i nal al kyn e. Thi s t er mi n a l
4
*
F o r co rr e sp on den ce
Electronic supplementary material: The online version of this article (https://doi.org/10.1007/s12039-019-1693-7) contains
supplementary material, which is available to authorized users.

4
Pa g e 2 o f 5
J. Chem. Sci. (2 020) 132 :4
O
COOH
NH2
HNO2
O
N2
K
O
COOH
Br
Pd(0)
O
K2CO
3
Pd
Br
Scheme 1. S yn th e ti c ba ck gr ou n d: S ynt he s i s of ben zyn e fr om 2- am in obenz oi c aci d.
O
H
H
COOH
H
R
Dimerisation
Pd(0)
O
R
R
Pd-cat
R
Br
Pd-Br
R
1
2
B
A
Scheme 2. Co n ce pt ual a ppro ach t owar ds t he s ynt hes i s of 1, 3-d iy ne s .
al k yn e wi l l d i m eri s e to pr o du c e 1, 3- di yn e un de r th e rea ct ion 3. Results and Discussion
co nd i t i o n s i n t h e pr es e nce of pa ll adi um cat al ys t
(
S che m e 2 ).
At fir s t , we h a ve f ocu s ed on th e s yn t he s is of b-b rom o
At th e be gi nnin g, we ha ve r ea c te d th e su bst r at e
b- br om o vi nyl c ar bo xyl ic a ci d wit h pa ll ad ium a c e ta te
a nd sod ium c ar bo na te in di me th ylf or ma mi de solv en t.
I n th is c as e, we ha ve ob ser ve d th e f or ma t ion of 1,4-
di phe nyl -1 ,3- di yne in 21 % of yi el d. The n we va r ie d
th e c at al yst s to im pr ov e th e r ea c ti on yi eld. W e
obs er ve d th at P d( PP h ) ga ve th e hi ghe st yi e ld a nd
v i ny l c ar b o x y l i c a ci ds s ta r tin g f ro m ac eto p he no ne der iv a-
t iv es . Th e Vi l s m ei e r -H aac k ty pe r eac tio n of ac etop he non e
g i ves b-b r o m o v i n yl al deh yd e de ri v at iv e ( 4) , w hi ch pr o-
d u ce s o u r d e si re d s ca ff ol d b- br om o vi ny l ca rb ox yl i c aci d
1
6
(
1 ) a ft er Pi n n i c k o xi da ti on ( Sc he m e 3 ) .
A f t er s y n t h e si z in g th e s ca ff ol d b- br o m o vi ny l car boxy l i c
3
4
P dC l2 di d no t pr om ote th e r ea c ti on. Th e n w e
e mp loye d di ff e r en t ba se s a nd f oun d th at C s CO dis -
aci d , we re a c t ed i t w ith di f fe re nt ca t al ys ts in v ar i ous s ol -
v ent s a n d t h e re s u l ts ar e s ho w n in Tab le 1 .
2
3
ti nc tly im pr ov ed th e yi el d. Am ong th e va r ious s ol-
ve nt s, DMF ga ve go od r es ult s. On in cr e a si ng the
r ea c ti on te m pe ra t ur e th e yi el d r em a ine d unc ha nge d;
ho weve r , de c re a sin g of te m pe ra t ur e to 60 °C re qui r ed
lo nge r r ea c ti on ti me wit h a lo wer yi el d. The r e for e , the
sc r ee ne d r ea c ti on c ondi tio ns we r e b- br om o viny l
H
R
COOH
Br
Pd cat., Base
solvent, heat
R
R
2
1
CH3
H
CHO
Br
H
COOH
Br
PBr , DMF
3
NaClO , NaH PO
4
2
2
o
Ph
O
CHCl , 0 C - r.t.
3
H O , H O
2
2
2
Ph
Ph
3
4
1
Scheme 3. S ynt he s i s o f s caf fol d.

J. Chem. Sci. (2 0 2 0 ) 1 32 :4
Table 1. S cr ee ni ng of th e r eac ti on con di t io ns .
P age 3 of 5
4
a
b
Sl . n o.
S o lv en t
Ca tal ys t
Ad dit i ve
Tem pe ra t ure ( °C )
Yi el d (% )
1
2
3
4
5
6
7
8
9
D MF
D MF
D MF
D MF
D MF
D MF
D MF
D MA
D MS O
D MF
D MF
P d( OA c )2
P dC l 2
P dC l ( PP h )
Na C O
2
Na C O
2
Na C O
2
Na C O
2
80
80
80
80
80
80
80
80
80
100
60
21
0
3
3
3
3
41
50
47
63
52
56
57
63
2
3 2
P d( P Ph 3 ) 4
P d( P Ph 3 ) 4
P d( P Ph 3 ) 4
P d( P Ph 3 ) 4
P d( P Ph 3 ) 4
P d( P Ph 3 ) 4
P d( P Ph 3 ) 4
P d( P Ph 3 ) 4
K C O
2
3
C s C O
2
3
NaO Ac
C s C O
C s C O
2
3
2
3
3
3
1
0
1
C s C O
2
C s C O
2
c
1
60
a
R ea ct io n co nd iti on s : s ca ff ol d b- br om o vi nyl car boxy l i c aci d (0 .5 m m ol ), cat al ys t (5 m ol % ),
b a se ( 1 eq ui va le nt) , s ol v en t ( 3 m L) a nd hea t ed fo r 2 h.
b
Is o l at ed yi el d.
c
Su b s t r ate va ni s he d af te r 6 h.
a
Table 2. Ex a mi n a ti on of th e s ub s t r ate s co pe .
O
H
R
H
R
COOH
Br
H
R
(II)
Pd
Pd(0)
OA
Base
Pd(II)
O
R
R
H
R
COOH
Br
RE
Pd(PPh ) , Cs CO
3
Pd-Br
3
4
2
R
R
1
C
B
Aerial
A
o
DMF, 80 C, 2h
oxidation
Pd(0)
2
RE
1
Entry
Substrate
Product
Yield (%)b
R
R
H
Ph
H
COOH
Br
2
1
2
Ph
Ph
63
1
a
2a
Scheme 4. P rob ab l e rea ct ion m ec han is m .
COOH
H
3
C
CH
3
61
Br
1b
c ar bo xyl ic a ci d ( 0.5 m mol ) , P d( PP h ) ( 5 mol %) ,
3 4
2b
3
H C
CH
3
C
s
C
O
(
1
m
m
o
l
)
h
e
a
t
e
d
a
t
8
0
°
C
i
n
D
M
F
s
o
l
v
e
n
t
2
3
H
H
COOH
Br
3
f
o
r
2
h
.
60
3
H C
A
f
t
e
r
g
e
t
t
i
n
g
t
h
e
s
c
r
e
e
n
e
d
r
e
a
c
t
i
o
n
c
o
n
d
i
t
i
o
n
s
,
w
e
1
c
H
3
C
2c
ha ve e mp loye d it on di ff e r en t sub sti tut ed b- br omo
vi nyl c ar bo xyl ic a ci d de r iva ti ve s a nd th e r es ul ts a r e
sho wn in Ta ble 2 . W e ha ve use d sub str a te s with va r -
io us sub sti tut ed a ry l r ing s a nd f oun d th at th e pr e se nc e
of e le ct r on- do nati ng gr ou ps on th e ph eny l r ing
de c re a se s th e yi el d of th e r ea c ti on ( Ta ble 2, e ntr y
COOH
4
MeO
OMe 55
Br
1d
2d
MeO
5
H
COOH
Br
6
1
2
–4 ) . W he n we pe r f or me d th e r ea c ti on wit h e le c tr on-
1e
2e
de fi ci en t a ry l r ing , th en th e yi el d wa s goo d ( Ta bl e 2 ,
e ntr y 7) . The ove r a ll yi el d of th e r ea c ti on w as
m ode r at e.
I n th is r ea c ti on, th e in situ ge ne r at ed te r min al
a ce ty le ne im m ed ia te ly di me r ise s in th e pr e senc e of
pa ll ad ium c at al yst . P ro ba bly th e r ea c ti on go e s in a
si mi la r wa y a s r ep or te d by Ya ng a nd c o- wor ke r s a nd
th en Ga zv oda et al., in a c oppe r - f re e S onoga s hir a
H
COOH
Br
6
62
1f
2
f
H
COOH
7
F
F
74
Br
1g
2g
F
1
7
a
r ea c ti on m ec ha ni sm . The pr ob abl e r ea c ti on me c ha -
ni sm is sho wn in S ch em e 4 .
Rea ct i o n c o nd i t i o n s : s ca ff ol d b- br om o vi ny l car boxy l i c
aci d (0 . 5 m m o l ), Pd ( PP h ) ( 5 m ol %) , Cs CO ( 1 equ iv a-
3
4
2
3
l en t) , DM F (3 m L) an d he at ed at 80 °C f or 2 h.
I so l a te d y i el d .
At fi rs t, th e P al la diu m ( 0) c at al yst un de r goe s
ox ida tiv e a ddi tio n wit h C -B r bon d in b- br omov inyl
b

4
Pa g e 4 o f 5
J. Chem. Sci. (2 020) 132 :4
c ar b o x y li c a c id de ri v at iv e ( Sch eme 4 , Co mpou nd 1) .
Th e n d e c a rb o x yl a t i on al o ng wi th r edu ct i ve e lim in a-
t i o n o f P d (II) g iv e s t he t er mi na l al k yn e B. Th e n P d( 0)
c at a ly s t u n d e rg o e s ae ri a l ox i da ti on t o Pd (I I ) whi ch
b i n ds wi th tw o a lk yn e i on s ge ne ra t ed i n t he pr e se nc e
o f th e b a s e . T h e re du ct i ve el i mi na ti o n o f t hi s di al kyne
Pd (II) s p e c ie s p ro d u ces t he fin al p ro du ct 1 ,3- diy ne a nd
Pd (0 ) c a ta ly s t re ge ne ra t ed.
L, Ho bb s A J W and Ho rs ham M A 198 7 H yd r oz i r -
con at i on m et hod s fo r nat u ral i s obut yl am i des ( an ac y -
cl i n, pel l i t ori ne and i ts vi nyl ogu e) and sy n t ho ns
Tetrahedron Lett. 28 487 5; (d ) Ho lm es A B , Tab or A B
and B aker R 199 1 Enan t i os el e ct i ve s ynt hes i s o f ( S) -
t ra ns - c-b ut enyny l c-am i n obu ty ri c aci d ( GABA)
J. Chem. Soc. Perkin Trans. 1 330 7; (e) Ho ye T R a nd
C ha ns on P R 199 3 S ynt he s i s of ( -)- bu l la taci n : T he
ena nt i om er of a po t ent , ant i t um o r, 4- hydr ox y l a te d ,
An no nac eo us acet og en i n Tetrahedron Lett. 34 5 04 3
. F C at ald o (Ed .) 200 5 Polyynes: Synthesis Properties,
and Applications (B oca R at on: C RC P res s / Ta y lo r &
F ran c i s )
. C r ow ley J D, Go ldu p S M, Lee A L, Lei gh D A a nd
McB ur ney R T 200 9 Act i ve m et al t em pl at e s ynt h es i s o f
ro t axa nes , cat ena ne s and m ol ecul ar s hut t l es Chem. Soc.
Rev. 38 153 0
5. (a) Gh ola mi M and Tyk win s k i R R 200 6 Ol i go m e r i c
and P ol ym eri c S y s t em s wi t h a C ros s - con ju ga t ed p-
F ram ewo rk Chem. Rev. 106 499 7; (b ) B axt e r P N W
and Dal i -Y oucef R 200 5 Ni t roge n Het er ocy cl i c Ca r -
b on- Ri ch Mat eri al s : S y nt hes i s and S pect ro s c op i c
P rop er t ie s of Deh ydr opy ri do annul ene Mac roc yc l es J.
Org. Chem. 70 493 5; (c) Mar s den J A and Hal ey M M
3
4
4
. Conclusions
In c o n c lu s io n , we h ave d eve l op ed a co n ce pt ua l
a p p ro a c h fo r th e sy nt h es is o f t er mi na l al k yn es f r om b-
b ro mo v in y l c a rbo xy l ic ac i ds u si ng pa l la di u m c at a-
1
8
l y s t . T h e g e n e ra t ed t er mi na l al k yn e di me ri s es in si tu
i n th e p re s e n c e o f p al la di u m ca t al ys t un d er t he sa m e
re a c ti o n c o n d it ion s. Fi n al ly , t he pr o du ct 1,4 -d i-
a ry lb u t a -1 ,3 - d iy ne was f or med i n mo de ra te t o go od
y i e l d s .
2
005 C arbo n Net wo rks B as ed on Deh ydr obenz o a n nu -
Supplementary Information (SI)
l ene s . 5. Ex t ens i on of Two -Di m ens i ona l C onj ug a t i on i n
Gr aph di yne Nan oarc hi t ect ure s J. Org. Chem. 70 1 02 13
. Di ede ri ch F , S t ang P J and R R Tyk win s k i 2 00 5
Acetylene Chemistry: Chemistry, Biology and Material
Science (W e i nhei m , Ger m any : Wi l ey- V C H Ve r l ag
Gm bH & C o. KG aA)
Ge n er a l re a ct i o n pr o ced ur e s , an al yti ca l da ta an d NM R
s p ect ra o f t h e c o m po un ds ar e av ai lab le at w ww .i as . ac.i n/
ch em s c i .
6
Acknowledgement
7. (a) Hal ey M M 200 8 S ynt he s i s and pr ope r t ie s o f
ann ul eni c s ubu ni t s of gr aph yne and gr ap h d iy n e
n ano archi t e ct ure s Pure Appl. Chem. 80 519 ; ( b) Oi sh i
T, Kat ay a m a T, Yam a g uch i K and Mi zuno N 2 00 9
Het er oge neo us l y C at aly ze d Effi ci ent Al kyn e– Al k yn e
Ho m oco upl in g by S upp ort ed C op per Hy dro x id e o n
Ti t ani um Ox ide Chem.–Eur. J. 15 753 9; (c) Adi m u rt h y
S , Mal aka r C C and B ei fus s U 200 9 In flu en ce of Ba se s
and Li gand s on t he Ou tco m e of t he C u(I )-Ca t a ly z ed
Ox i dat i ve Ho mo co upl i n g of Ter m in al Al kyn es t o 1 ,4 -
Di s ubs t i tu ted 1, 3-D i ynes Us i ng Ox ygen as an Ox i d an t
J. Org. Chem. 74 564 8; (d ) Zhen g Q, Hu a R and Wa n Y
I wo u l d l i k e t o t h an k D ST- S ERB , G ov ern m en t of I ndi a fo r
fi n an c i a l s u p p o r t o f th is pr o jec t ( Fi le N o.: ECR / 2017 /
0 0 0 3 9 6 ) a n d DS T-F I ST , G ov e r nm en t of I nd i a f or s pon s o r-
i n g d e pa r t m en t a l res e ar c h f aci l it ie s.
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017 A nov el Zi nc-c ata ly zed C ad i ot -C hodk i ew ic z

J. Chem. Sci. (2 0 2 0 ) 1 32 :4
P age 5 of 5
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1 . W an g S , Yu L, L i P , M en g L a n d W a n g L 2 01 1 C o p-
pe r ( I) I o di de C a ta ly ze d Cr o ss -C o u pl i n g R e ac t i o n o f T e r- 18. Gen eral rea c t io n con di ti on: b-b rom o vi nyl ca rb o xy l i c
mi nal A lkyn es w ith 1-Br omo alkynes : A Si mple S ynt he s is
o f Un s y m m e t ri ca l Bu ta -1, 3-d iyn es Synthesis 15 41
aci d (0 .5 m m ol ), P d(P P h 3 ) 4 (5 m ol % ), C s CO ( 1
2 3
m m ol ) wer e t ake n i n a t wo nec k ro und bot t om e d fla sk
and t hen 3 m L of di m et hyl f orm am i de (D MF ) so l u t i on
was add ed. The rea ct i on m i xt u re was t hen hea t e d a t 8 0
°C fo r 2 h. Af te r com p let i on of t he rea ct ion , mi x t ur e
was al l owed t o coo l t o ro om t em per at ure a nd t he n
di l ut ed wi t h wat er . Then t he pr oduc t was e xt r ac t ed
wi t h et hyl acet at e (3 x 20 m L) . Th e com bi ned o rg an i c
l ayer was eva por at ed und er red uc ed pr es s ur e a nd t he
cru de pr oduc t was pur i fi ed by col u m n chr om ato g r a ph y
us i ng s i li ca gel (6 0–12 0 m es h) and h exa ne/ eth yl a ce t -
at e as el uent
1
2 . Ah a m m ed S, K un d u D an d Ra nu B C 20 14 C u- C at -
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s p 2
s p
s p
s p
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Chem. 79 7 3 9 1
1
3 . Huang Z, Shang R, Zhang Z R, Tan X D, Xiao X and Fu
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4 . Lo g u l lo F M , S eit z A M an d F ri e dm a n L 19 68 ben -
z en e d ia z on i u m -2 - car bo xy la te an d bi ph en yl ene Org.
Synth. 48 1 2
1