Terminal Alkynes from Acros Organics are versatile building blocksThe 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 C CH R R1 X R 2 R3 R1 R C R2 R3R H

C

C

-

R1 O H R1 R C C H

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 CH1

O

Zn(OTf)2 NEt3 Ph CH3 NMe2 R

OH C C R1

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.

HO Zn(OTf)2 AO 31709

N C +

CH

Copper(I)triflate Pybox

HN C C

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

(+)-N-Methylephedrine

AO 41431

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]

Ethyl ethynyl carbinol 99%H3C OH

CH

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

Ethyl propiolate 99% Ethyl propiolate 97%HC

O O CH3

1-Ethynyl-1-cyclohexanol 99+%

OH

CH

1 2

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.

12753 [555-57-7] 13145[107-19-7] 13146 [2450-71-7] 13147 [15430-52-1] 13148 [106-96-7] 13149

N-Methyl-Npropargylbenzylamine 97%Propargyl alcohol 99%HO

N CH CH3

CH

mono-Propargylamine 99%H2N

CH

mono-Propargylamine hydrochloride 95% Propargyl bromide, 80 wt% solution in toluene, stabilized

Cl

-

H3N

+

CH

CH BrO CH N O

N-(Propargyloxy)phthalimide 98%

[4616-63-19] 13150 [471-25-0] 15246 [536-74-3] 15572 [818-72-4] 15682[115-19-5] 15733 [927-74-2] 15734[17356-19-3] 16006 [77-75-8] 16225 [7223-38-3] 17134 [871-84-1] 17135 [2396-65-8] 17404

O

Propiolic acid 98%HO

O

CH

Phenylacetylene 98%

CH

1-Octyn-3-ol 96%

CH H3C OH

2-Methyl-3-butyn-2-ol 98%H3C

CH3 CH OH

3-Butyn-1-ol 97%

HC OH

1-Ethynylcyclopentanol 98%

OH CH

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

OH CH

1-Dimethylamino-2-propyne 97%

H3C N H3C CH

1,7-Octadiyne 99%

HC

CH

1,8-Nonadiyne 98%HC CH

Methyl propiolate 99%

HC O CH3HC

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

1,1-Diethylpropargylamine 97%

NH2 H3C CH3

Lithium acetylide ethylenediamine complex 85%HC

H2NLi

[6867-30-7]

NH2

19969 [127-66-2] 20357 [1066-54-2] 21016 [2091-46-5] 21373 [6089-09-4] 22342[14267-92-6] 22343 [764-93-2] 22344[917-92-0] 22345[765-03-7] 22346[628-71-7] 22351[629-05-0] 22719 [72-33-3] 29424 [994-89-8] 29567 [1945-84-2] 30382

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

OH

CH3 CH

Trimethylsilylacetylene 98%H3C

CH3 Si CH3 CH

Propargyltriphenylphosphonium bromide 99+% 4-Pentynoic acid 98%HC

P+ CH Br-

O

OH

5-Chloro-1-pentyne 98%

HC

Cl

22343 1-Decyne 98% [764-93-2]3,3-Dimethyl-1-butyne 98%

H3C

CH

H3C H3C

CH3

CH

1-Dodecyne 98%

HC

CH3

1-Heptyne 99%

HC

CH3

1-Octyne 99%

HC

CH3

Ethynylestradiol 3-methyl ether 97%H3C O

HC OH

Tributylethynylstannane 98%HC Sn H3C

CH3 CH3

2-Ethynylpyridine 98+%N CH

1-Pentyne 99%

HC CH3

[627-19-0] 30737 [14918-21-9] 30739 [927-80-0] 30942 [2396-63-6] 31390 [5582-62-7] 32990

5-Hexynenitrile 98%

HC

N

Ethyl ethynyl ether, solution in hexanes 1,6-Heptadiyne 98%

50

wt%

H3C O CH

HC

CH

Propargyloxytrimethylsilane 97%HC

H3C Si O

CH3 CH3CH

1-Hexyne 98%

H3C

[693-02-7]

33043 [5390-04-5] 33044

4-Pentyn-1-ol 95%

HC

OH

3-Butyn-2-one 96%HC

O

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

CH3

3-Cyclopentyl-1-propyne 98%HC

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

HC CH2 CH3

[78-80-8] 34203 [1066-26-8] 34453[3230-69-1] 35098

Sodium acetylide, 18 wt% slurry in xylene3-Methyl-1-penten-4-yn-3-ol 99%

HC

Na

OH HC CH3 OH CH2

1-Heptyn-3-ol 98%HC

CH3

[7383-19-9] 35187

1,9-Decadiyne 98%

HC

CH

[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]

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

,

O HC HN OH O O

,HC HN

O OH O O H3C CH3 CH3

(S)-(-)-3-Butyn-2-ol , 95%, (98% e.e.)(S)-1-Octyn-3-ol e.e.) , 95%, (98%

OH HC CH3CH3 HO

HC

(R)-N-FMOC-proparylglycine 95%, (98% e.e.) (R)-N-BOC-Propargylglycine 95%, (98% e.e.) (R)-1-Octyn-3-ol e.e.) ,

,

O HC HN OH O O

,HC HN

O OH O O H3C CH3 CH3

95%, (98%

H3C OH

CH

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

CF 3

CH

3-Aminophenylacetylene 98%

CH H2N

Propargyltrimethylsilane, stabilized 90%HC H3C

CH3 Si CH3HO CH H3C

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

36913 [6746-94-7] 36874

Ethynylcyclopropane 98%

CH

(Triisopropylsilyl)acetylene 97%

H3C H3C Si H3C H3C

CH3 CH CH3

[89343-06-6] 37137

1-Ethynyl-4-fluorobenzene 98%F

CH

[766-98-3] 36873[1777-03-3] CD06185

(Triethylsilyl)acetylene 97%Si H3C

CH3 CH CH3

1,3-Dichloro-2-(prop-2ynyloxy)benzene N-Prop-2-ynylureaH2N

Cl

O CH Cl

[3598-66-1] CD11100 [5221-62-5] KM06575

O

NH

CHH3C CH3 O

4-[(1,1-Dimethylprop-2ynyl)oxy]benzonitrile 3-Butyn-2-ol 97%

[33143-92-9] 24531 [2028-63-9] BTB09894

N

CH

OH H3C CH

1-Eth-1-ynyl-4-(hexyloxy)benzeneH3C O

CH

[79887-17-5] BTB09895 [79887-16-4] BTB09896 [79887-15-3] BTB09897 [39604-97-2] BTB09899

1-Eth-1-ynyl-4(pentyloxy)benzeneH3C O

CH

1-Butoxy-4-eth-1-ynylbenzeneH3C OO CH

CH

1-Eth-1-ynyl-4-propoxybenzeneH 3C

4-EthynylanisoleO CH3

CH

[768-60-5] BTB09901 [79887-12-0] BTB09902

1-Ethynyl-4-heptylbenzeneH3C

CH

1-Eth-1-ynyl-4-hexylbenzeneH3C

CH

[79887-11-9] BTB09904 [79887-09-5] BTB09905 [62452-73-7] BTB09906[40307-11-7] BTB09984 [29079-00-3]

1-Butyl-4-eth-1-ynylbenzeneH3C

CH

1-Eth-1-ynyl-4-propylbenzeneCH H3C

1-Ethyl-4-eth-1-ynylbenzeneCH H3C

4-Ethynyl-1,1'-biphenyl

CH

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

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

H3C CH3 HO

CH3

CH

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

,

HC

Mg BrCH

97%,

1-Chloro-4-ethynylbenzene 98%Cl

CH

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

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

CH N

O O

S