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Terminal Alkynes from Acros Organics are versatile building blocks

The major reactions are the electrophilic additions to the triple bond 1 , nucleophilic additions and substitutions by acetylide-carbanions and coupling reactions of terminal alkynes.

OH

R 1 C H C R
R
1
C
H
C
R

Base

R C C - O R 1 H X R 1 R 2 R 3
R C
C -
O
R 1
H
X
R 1
R 2 R 3
R
1
R
C
R 2
R 3

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

be easily deprotonated by stronger bases and the

corresponding carbanions are useful nucleophiles for

addition reactions and nucleophilic substitution

reactions.

R

C

CH

R

1

CH

O

R H
R
H
OH Zn(OTf) 2 NEt 3 R C Ph CH 3 C
OH
Zn(OTf) 2
NEt 3
R
C
Ph
CH 3
C

HO

NMe 2

R 1

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 excess

2

.

N CH C + Copper(I)triflate benzene complex AO 37109 (R)-Pybox AO 36843 (S)-Pybox AO 36844
N
CH
C
+
Copper(I)triflate benzene complex AO 37109
(R)-Pybox AO 36843 (S)-Pybox AO 36844
HN C C
HN
C
C

Copper(I)triflate

Pybox

Zn(OTf) 2

(+)-N-Methylephedrine

AO 31709

Copper catalyzed

asymmetric addition of

terminal alkynes with to imines leads to propargylamines 3

AO 41431

AO 21607

(-)-N-Methylephedrine

Copper catalyzed coupling reactions of terminal alkynes are well known since many years (i.e. Glaser

Coupling

catalysed cross coupling reaction of terminal

alkynes with alkenyl or aryl halides (Stephens

Castro-Reaction 7 ,

again attracted a lot of attention.

4

, Hay reaction, Eglington Reaction 5 , Cadiot-Chodkiewicz Coupling 6 ) but the palladium

8

Sonogashira reaction ) has

6 ) but the palladium 8 Sonogashira reaction ) has B r HC C R Pd-catalyst,

Br

HC C R Pd-catalyst, Cu-salt
HC
C
R
Pd-catalyst, Cu-salt
C C
C
C

R

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

Ethyl ethynyl carbinol 99%

[4187-86-4]

11890

Ethyl propiolate 99%

SB01463

Ethyl propiolate 97%

[623-47-2]

11910

1-Ethynyl-1-cyclohexanol 99+%

[78-27-3]

H C

3

CH 11910 1-Ethynyl-1-cyclohexanol 99+% [78-27-3] H C 3 OH O CH 3 O HC OH CH 1

OH

O

CH 3 O HC OH CH
CH 3
O
HC
OH
CH

1 See many examples in: J.March, Advanced Organic Chemistry, J.Wiley&Sons, New York 1985

2 A) D. E. Frantz, R. Fässler, 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

4

C. Wei and C.-J. Li J. Am. Chem. Soc., 2002, 124 ,5638 -5639.

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

6

Organic Syntheses, Coll. Vol. 5, p.517; Vol. 45, p.39

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.

12753

N-Methyl-N-

propargylbenzylamine 97%

[555-57-7]

13145

Propargyl alcohol 99%

[107-19-7]

13146

mono-Propargylamine 99%

[2450-71-7]

13147

mono-Propargylamine hydrochloride 95%

[15430-52-1]

13148

Propargyl bromide, 80 wt% solution in toluene, stabilized

[106-96-7]

13149

N-(Propargyloxy)phthalimide 98%

[4616-63-19]

13150

Propiolic acid 98%

[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%

[115-19-5]

15733

3-Butyn-1-ol 97%

[927-74-2]

15734

1-Ethynylcyclopentanol 98%

[17356-19-3]

16006

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

[77-75-8]

16225

1-Dimethylamino-2-propyne 97%

[7223-38-3]

17134

1,7-Octadiyne 99%

[871-84-1]

17135

1,8-Nonadiyne 98%

[2396-65-8]

17404

Methyl propiolate 99%

[922-67-8]

17563

1,1-Diethylpropargylamine 97%

[3234-64-8]

18125

Lithium acetylide ethylenediamine complex 85%

[6867-30-7]

N CH CH 3 CH HO CH H N 2 CH + H N 3
N
CH
CH 3
CH
HO
CH
H N
2
CH
+
H N
3
Cl -
Br
CH
O N O O
O
N
O
O

HO

O

CHHO CH H N 2 CH + H N 3 Cl - Br CH O N

CH

CH C H

CH H C 3 OH CH 3 H C CH 3
CH
H C
3
OH
CH 3
H C
CH
3

OH

HC OH OH CH
HC
OH
OH
CH

OH

H C CH 3 H C 3 H C 3 N H C 3 CH
H
C
CH
3
H
C
3
H
C
3
N
H
C
3
CH
HC
CH
HC
CH
HC
O
CH 3
HC
NH 2
CH 3
H C
3
H N
2
NH 2
HC
Li

19969

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

[127-66-2]

20357

Trimethylsilylacetylene 98%

 

[1066-54-2]

21016

Propargyltriphenylphosphonium bromide 99+%

[2091-46-5]

21373

4-Pentynoic acid 98%

 

[6089-09-4]

22342

5-Chloro-1-pentyne 98%

 

[14267-92-6]

22343

22343 1-Decyne 98%

 

[764-93-2]

[764-93-2]

22344

3,3-Dimethyl-1-butyne 98%

 

[917-92-0]

22345

1-Dodecyne 98%

[765-03-7]

22346

1-Heptyne 99%

[628-71-7]

22351

1-Octyne 99%

[629-05-0]

22719

Ethynylestradiol

3-methyl

ether

97%

[72-33-3]

29424

Tributylethynylstannane 98%

 

[994-89-8]

29567

2-Ethynylpyridine 98+%

 

[1945-84-2]

30382

1-Pentyne 99%

[627-19-0]

30737

5-Hexynenitrile 98%

 

[14918-21-9]

30739

Ethyl ethynyl ether, 50 wt% solution in hexanes

[927-80-0]

30942

1,6-Heptadiyne 98%

 

[2396-63-6]

31390

Propargyloxytrimethylsilane 97%

[5582-62-7]

32990

1-Hexyne 98%

[693-02-7]

OH CH 3 CH H C CH 3 CH 3
OH
CH 3
CH
H C
CH 3
CH
3

CH 3

P + CH Br - HC O OH HC Cl H 3 C CH H
P +
CH
Br -
HC
O
OH
HC
Cl
H 3 C
CH
H C
3
CH 3
H C
3
CH
HC
CH 3
CH 3 HC HC CH 3
CH 3
HC
HC
CH 3
HC OH H C 3 O CH 3 CH 3 HC Sn H C 3
HC
OH
H C
3
O
CH 3
CH 3
HC
Sn
H C
3
N
CH
HC
CH 3
HC
N
H C
3
O
CH
HC
CH
H C
3
CH 3
Si
O
CH 3
HC
H C
3
CH

33043

4-Pentyn-1-ol 95%

[5390-04-5]

33044

3-Butyn-2-one 96%

 

[1423-60-5]

33606

3-Cyclopentyl-1-propyne 98%

[116279-08-4]

33648

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

 

[78-80-8]

34203

Sodium acetylide, 18 wt% slurry in xylene

[1066-26-8]

34453

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

[3230-69-1]

35098

1-Heptyn-3-ol 98%

 

[7383-19-9]

35187

1,9-Decadiyne 98%

 

[1720-38-3]

36150

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

[-]

36180

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

[63039-48-5]

36241

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

[2914-69-4]

36243

(S)-1-Octyn-3-ol

,

95%,

(98%

e.e.)

[32556-71-1]

36262

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

[-]

36285

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

[63039-46-3]

36317

(R)-1-Octyn-3-ol

,

95%,

(98%

e.e.)

[32556-70-0]

36409

1,1,1-Trifluoro-2-phenyl-3-butyn-

2-ol 95%

[99727-20-5]

36472

3-Aminophenylacetylene 98%

[54060-30-9]

36663

Propargyltrimethylsilane, stabilized 90%

 

[13361-64-3]

36630

(R)-(+)-3-Butyn-2-ol

,

98%,(98%

e.e.)

[42969-65-3]

HC

ol , 98%,(98% e.e.) [42969-65-3] HC O OH HC CH 3 HC HC CH 2 CH

O

OH

HC CH 3 HC HC CH 2 CH 3 HC Na
HC
CH 3
HC
HC
CH 2
CH 3
HC
Na

OH

HC CH 2 CH 3 OH CH 3 HC HC CH
HC
CH 2
CH
3
OH
CH 3
HC
HC
CH
O HC OH HN O O O OH HC CH 3 HN O CH 3
O
HC
OH
HN
O
O
O
OH
HC
CH 3
HN
O
CH 3
H C
O
3

OH

HC CH 3 CH 3 HO HC
HC
CH 3
CH 3
HO
HC
O HC OH HN O O O OH HC CH 3 HN O CH 3
O
HC
OH
HN
O
O
O
OH
HC
CH 3
HN
O
CH 3
H C
O
3
H 3 C
OH
CH
CF 3
HO
CH
CH
H 2 N
CH 3
Si
HC
CH 3
H C
3

HO

H C 3
H C
3

CH

36913

Ethynylcyclopropane 98%

[6746-94-7]

36874

(Triisopropylsilyl)acetylene 97%

[89343-06-6]

37137

1-Ethynyl-4-fluorobenzene 98%

[766-98-3]

36873

(Triethylsilyl)acetylene 97%

[1777-03-3]

CD06185

1,3-Dichloro-2-(prop-2-

ynyloxy)benzene

[3598-66-1]

CD11100

N-Prop-2-ynylurea

[5221-62-5]

KM06575

4-[(1,1-Dimethylprop-2-

ynyl)oxy]benzonitrile

[33143-92-9]

24531

3-Butyn-2-ol 97%

[2028-63-9]

BTB09894

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

[79887-17-5]

BTB09895

1-Eth-1-ynyl-4-

(pentyloxy)benzene

[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

[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

[62452-73-7]

BTB09906

1-Ethyl-4-eth-1-ynylbenzene

[40307-11-7]

BTB09984

4-Ethynyl-1,1'-biphenyl

[29079-00-3]

CH H C CH 3 3 H C 3 Si CH H C 3 H
CH
H
C
CH
3
3
H
C
3
Si
CH
H
C
3
H
C
CH
3
3
CH F CH
CH
F
CH

Cl

O3 3 H C 3 Si CH H C 3 H C CH 3 3 CH

Cl

O

CH

H N 2 NH CH CH 3 H 3 C N O CH
H N
2
NH
CH
CH 3
H 3 C
N
O
CH

OH

H 3 C CH CH H 3 C O CH H 3 C O CH
H 3 C
CH
CH
H 3 C
O
CH
H 3 C
O
CH
H 3 C
O
O
C
H
H C
3
CH
O

CH 3

CH H 3 C CH
CH
H 3 C
CH

H 3 C

CH H 3 C H C 3 CH H C 3
CH
H 3 C
H
C
3
CH
H
C
3

CH

O CH H 3 C O CH H 3 C O O C H H C

CH

37155

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

[107-54-0]

37744

Ethynylmagnesium chloride , 1.1M solution in THF/toluene

[65032-27-1]

37680

3-Phenyl-1-propyne

97%,

stabilized

[10147-11-2]

37706

1-Chloro-4-ethynylbenzene 98%

[873-73-4]

DFP00032

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

[10442-03-2]

CH 3 H C 3 CH 3 HO CH HC M g
CH 3
H C
3
CH 3 HO
CH
HC
M g

Br

CH 4-Prop-2-ynyl-thiomorpholine 1,1- dioxide 97+% [10442-03-2] CH 3 H C 3 CH 3 HO CH HC M

CH Cl DFP00032 4-Prop-2-ynyl-thiomorpholine 1,1- dioxide 97+% [10442-03-2] CH 3 H C 3 CH 3 HO CH HC

CH 4-Prop-2-ynyl-thiomorpholine 1,1- dioxide 97+% [10442-03-2] CH 3 H C 3 CH 3 HO CH HC M

O