Terminal Alkynes
Terminal Alkynes
Terminal Alkynes
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
C
R2
R3
R
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 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
11849
[4187-86-4]
CH
11890
SB01463
[623-47-2]
11910
[78-27-3]
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
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
Br
CH
N-(Propargyloxy)phthalimide 98%
CH
N
[4616-63-19]
13150
CH
H3N
[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]
CH
HC
O
CH3
1,1-Diethylpropargylamine 97%
HC
NH2
H3C
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
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
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%
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
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
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
CH
N
S
O