Terminal Alkynes from Acros Organics are versatile building blocks

The major reactions are the electrophilic additions to the triple bond1, nucleophilic additions and
substitutions by acetylide-carbanions and coupling reactions of terminal alkynes.
OH
Base
R

CH

R1

R1

H
X

R1

R 2 R3
R1

Due to their relatively high acidity (pKa ~ 25) they can

be easily deprotonated by stronger bases and the
corresponding carbanions are useful nucleophiles for
addition reactions and nucleophilic substitution
reactions.
R
CH
1

C
R2

R3
R

In the presence of zinctriflate, a base and N-methylephedrine as

chiral auxiliary the addition of terminal acetylenes with aldehydes
leads to propargylic alcohols with high enantiomeric excess2.

OH

Zn(OTf)2

NEt3
Ph

CH3

C
C
R1

HO

NMe2

Zn(OTf)2 AO 31709
(+)-N-Methylephedrine

CH
C
+

Copper(I)triflate

HN

Pybox
C
C

AO 41431

Copper catalyzed
(-)-N-Methylephedrine
AO 21607
asymmetric addition of
terminal alkynes with to imines leads to propargylamines3

Copper(I)triflate benzene complex AO 37109

(R)-Pybox AO 36843 (S)-Pybox AO 36844

Copper catalyzed coupling reactions of terminal alkynes are well known since many years (i.e. Glaser
Coupling4, Hay reaction, Eglington Reaction5, Cadiot-Chodkiewicz Coupling6) but the palladium
catalysed cross coupling reaction of terminal
Br
HC C R
alkynes with alkenyl or aryl halides (Stephens
7
8
C C R
Castro-Reaction , Sonogashira reaction ) has
Pd-catalyst, Cu-salt
again attracted a lot of attention.
More details on the Sonogashira-reaction and other cross coupling reactions are available in the Acros
broschure Metal catalysts; ask for your free copy

Acros Organics offers a wide range of terminal alkynes

11849
[4187-86-4]

CH

Ethyl ethynyl carbinol 99%

H3C
OH

11890
SB01463
[623-47-2]
11910
[78-27-3]

Ethyl propiolate 99%

Ethyl propiolate 97%

CH3

HC

1-Ethynyl-1-cyclohexanol 99+%

OH

CH

See many examples in: J.March, Advanced Organic Chemistry, J.Wiley&Sons, New York 1985
A) D. E. Frantz, R. Fssler, E. M. Carreira, J. Am. Chem. Soc., 2000, 122, 1806-1807; B) D. Boyall,
D. Frantz, E. M. Carreira, Org. Lett., 2002, 4, 2605-2606; E.M.Carreira, Chimia, 55 (2001) 818.
3
C. Wei and C.-J. Li J. Am. Chem. Soc., 2002, 124 ,5638 -5639.
4
C. Glaser, Liebigs.Ann.d.Chem, 154, 137 (1870); Ber.d.dt.chem.Ges. 2, 422 (1869).
T. Gibtner, F. Hampel, J.-P.Gisselbrecht, A. Hirsch, Chem. Eur. J., 2002, 68, 408-432.
5
Organic Syntheses, Coll. Vol. 5, p.517; Vol. 45, p.39
6
A recent example: C. Garcia, P. J. Walsh, J. Org. Chem., 2002, 67, 6841-6844
7
A) C.E.Castro, R.D.Stephens, J.Org.Chem. 28 (1963) 2163; B) C.E.Castro, R.D.Stephens,
J.Org.Chem. 28 (1963) 3313.
8
K.Sonogashira, Y. Tohda, N.Higara, Tetrahedron Lett. (1975) 4467.
2

12753
[555-57-7]
13145

N-Methyl-Npropargylbenzylamine 97%

N
CH
CH3

Propargyl alcohol 99%

CH
HO

[107-19-7]
13146

mono-Propargylamine 99%

CH
H2N

[2450-71-7]
13147
[15430-52-1]
13148
[106-96-7]
13149

mono-Propargylamine
hydrochloride 95%

Cl

Propargyl bromide, 80 wt%

solution in toluene, stabilized

Br

CH

N-(Propargyloxy)phthalimide 98%

CH
N

[4616-63-19]
13150

CH

H3N

Propiolic acid 98%

HO

[471-25-0]
15246

Phenylacetylene 98%

[536-74-3]
15572

1-Octyn-3-ol 96%

[818-72-4]
15682

2-Methyl-3-butyn-2-ol 98%

CH
CH

CH
H3C
OH

CH3
H3C

[115-19-5]
15733
[927-74-2]
15734
[17356-19-3]
16006

CH
OH

3-Butyn-1-ol 97%

HC
OH

1-Ethynylcyclopentanol 98%

OH
CH
OH

3-Methyl-1-pentyn-3-ol 99+%
H3C

[77-75-8]
16225

CH

H3C

1-Dimethylamino-2-propyne 97%

H3C
N
H3C

[7223-38-3]
17134

1,7-Octadiyne 99%

[871-84-1]
17135

1,8-Nonadiyne 98%

CH

HC

CH
HC

[2396-65-8]
17404

[922-67-8]
17563
[3234-64-8]
18125

[6867-30-7]

Methyl propiolate 99%

CH

HC
O
CH3

1,1-Diethylpropargylamine 97%

HC

NH2
H3C

Lithium acetylide ethylenediamine

complex 85%
HC

CH3

H2N
Li

NH2

19969
[127-66-2]
20357

OH

DL-2-Phenyl-3-butyn-2-ol 98+%

CH3 CH

CH3

Trimethylsilylacetylene 98%
H3C

[1066-54-2]
21016

Propargyltriphenylphosphonium
bromide 99+%
4-Pentynoic acid 98%

HC

[6089-09-4]
22342

5-Chloro-1-pentyne 98%

HC

22343 1-Decyne 98%

[764-93-2]

H3C

[764-93-2]
22344

CH

P+

[2091-46-5]
21373

[14267-92-6]
22343

Si
CH3

CH
Br-

OH

Cl
CH

H3C

3,3-Dimethyl-1-butyne 98%

CH3

H3C

[917-92-0]
22345

1-Dodecyne 98%

HC

[765-03-7]
22346

1-Heptyne 99%

HC

[628-71-7]
22351

1-Octyne 99%

HC

[629-05-0]
22719
[72-33-3]
29424

CH
CH3

[1945-84-2]
30382

[627-19-0]
30737
[14918-21-9]
30739

CH3

HC

Ethynylestradiol 3-methyl ether

97%

OH

H3C

CH3

Tributylethynylstannane 98%

CH3
HC

[994-89-8]
29567

CH3

Sn

H3C

2-Ethynylpyridine 98+%
N
CH

1-Pentyne 99%

HC
CH3
HC

5-Hexynenitrile 98%

Ethyl ethynyl ether,

solution in hexanes

50

wt%

[927-80-0]
30942

1,6-Heptadiyne 98%

[2396-63-6]
31390

Propargyloxytrimethylsilane 97%

H3C
O

CH

HC

CH

H3C
Si

[5582-62-7]
32990

[693-02-7]

O
HC

1-Hexyne 98%

H3C

CH3
CH3
CH

33043

4-Pentyn-1-ol 95%

[5390-04-5]
33044

3-Butyn-2-one 96%

HC

OH
O
HC

[1423-60-5]
33606
[116279-08-4]
33648

[78-80-8]
34203
[1066-26-8]
34453

CH3

3-Cyclopentyl-1-propyne 98%
HC

2-Methyl-1-buten-3-yne 98%

HC

Sodium acetylide, 18 wt% slurry

in xylene

HC

CH2
CH3

Na

OH

3-Methyl-1-penten-4-yn-3-ol 99%
HC

[3230-69-1]
35098

CH2

CH3
OH

1-Heptyn-3-ol 98%

CH3

[7383-19-9]
35187

[1720-38-3]
36150
[-]
36180
[63039-48-5]
36241
[2914-69-4]
36243
[32556-71-1]
36262
[-]
36285
[63039-46-3]
36317
[32556-70-0]
36409
[99727-20-5]
36472
[54060-30-9]
36663
[13361-64-3]
36630
[42969-65-3]

HC

1,9-Decadiyne 98%

HC

(S)-N-FMOC-Propargylglycine
95%, (98% e.e.)

CH

O
HC
OH

HN

O
O

(S)-N-BOC-Propargylglycine
95%, (98% e.e.)

OH
HC
HN

CH3

CH3

O H3C

(S)-(-)-3-Butyn-2-ol , 95%, (98%

e.e.)

OH
HC
CH3

(S)-1-Octyn-3-ol
e.e.)

95%,

(98%

CH3
HO

HC

(R)-N-FMOC-proparylglycine
95%, (98% e.e.)

O
HC
OH

HN

O
O

(R)-N-BOC-Propargylglycine
95%, (98% e.e.)

OH
HC
HN

CH3
CH3

O H3C

(R)-1-Octyn-3-ol
e.e.)

95%, (98%

H3C
OH

CH

1,1,1-Trifluoro-2-phenyl-3-butyn2-ol 95%

CF 3
HO

3-Aminophenylacetylene 98%

CH

CH
H2N

CH3

Propargyltrimethylsilane,
stabilized 90%

Si
HC

(R)-(+)-3-Butyn-2-ol , 98%,(98%
e.e.)

CH3

H3C

HO
CH
H3C

36913

Ethynylcyclopropane 98%

[6746-94-7]
36874

(Triisopropylsilyl)acetylene 97%

CH

CH3

H3C
H3C
Si
H3C
H3C

[89343-06-6]
37137

1-Ethynyl-4-fluorobenzene 98%

[766-98-3]
36873

(Triethylsilyl)acetylene 97%

CH
CH3

CH

F
CH3
Si

[1777-03-3]
CD06185

[3598-66-1]
CD11100

CH

H3C
CH3
Cl

1,3-Dichloro-2-(prop-2ynyloxy)benzene

O
CH
Cl

N-Prop-2-ynylurea
H2N

[5221-62-5]
KM06575

[33143-92-9]
24531

NH

4-[(1,1-Dimethylprop-2ynyl)oxy]benzonitrile

CH
CH3

H3C
N

CH

OH

3-Butyn-2-ol 97%
H3C

[2028-63-9]
BTB09894

[79887-17-5]
BTB09895

CH

CH

1-Eth-1-ynyl-4-(hexyloxy)benzene
H3C

CH

1-Eth-1-ynyl-4(pentyloxy)benzene
H3C

[79887-16-4]
BTB09896

1-Butoxy-4-eth-1-ynylbenzene

[79887-15-3]
BTB09897

1-Eth-1-ynyl-4-propoxybenzene

[39604-97-2]
BTB09899

4-Ethynylanisole

CH

H3C

O
O

H 3C

CH

CH

[768-60-5]
BTB09901

1-Ethynyl-4-heptylbenzene

[79887-12-0]
BTB09902

1-Eth-1-ynyl-4-hexylbenzene

[79887-11-9]
BTB09904

1-Butyl-4-eth-1-ynylbenzene

[79887-09-5]
BTB09905

1-Eth-1-ynyl-4-propylbenzene

CH3
CH

H3C

CH

H3C

CH

H3C

CH

[62452-73-7]
BTB09906

H3C

1-Ethyl-4-eth-1-ynylbenzene
CH

[40307-11-7]
BTB09984
[29079-00-3]

H3C

4-Ethynyl-1,1'-biphenyl

CH

37155
[107-54-0]
37744
[65032-27-1]
37680
[10147-11-2]
37706

[873-73-4]
DFP00032
[10442-03-2]

3,5-Dimethyl-1-hexyn-3-ol 99%

CH3

H3C
CH3 HO

Ethynylmagnesium chloride
1.1M solution in THF/toluene
3-Phenyl-1-propyne
stabilized

HC

CH

Mg
Br
CH

97%,

CH

1-Chloro-4-ethynylbenzene 98%
Cl

4-Prop-2-ynyl-thiomorpholine 1,1dioxide 97+%

CH
N

S
O