C≡C BOND FORMATION 115

C≡C Bond Formation

1. From other acetylenes

2. From carbonyls
3. From olefins
4. From Strained Rings
5. Eschenmosher Fragmentation
6. Allenes

From Other Acetylenes

- The proton of terminal acetylenes is acidic (pKa= 25), thus they can be
deprotonated to give acetylide anions which can undergo substitution reactions
with alkyl halides, carbonyls, epoxides, etc. to give other acetylenes.
R R1

R1-X
O
OH
R _ R2 R3
R H R
R
M+ R2 3

Et2AlCl
OH
R

- Since the acetylenic proton is acidic, it often needs to be protected as a

trialkylsilyl derivative. It is conveniently deprotected with fluoride ion.
B:, R3SiCl F-
R H R SiR3 R H

Acetylide anions and organoboranes

_ R3B _ I2 JOC 1974, 39 , 731

R1 Li+ R1 BR3 Li+ R1 R JACS, 1973, 95 , 3080

Palladium Coupling Reactions:

O O
O O

JACS 1990,
Cl Cl
iPr3Si SnBu3 112, 1607
(Ph3P)4Pd
iPr3Si SiiPr3
 C≡C BOND FORMATION 116

OTBS
OTBS CO2Me
CO2Me Br C5H11
OTBS
OTBS OTBS
Pd(Ph3P)4, CuI
iPr2NH, PhH

TBSO C5H11 JACS 1985,

107, 7515

OH
HO
CO2H
OH

Copper Coupling- 1,3-diynes

Cu(OAc)2 Adv. Org. Chem.
R1 + R2 R1 R1 1963,4 , 63

Nicholas Reaction
- acetylenes as their Co2(CO)8 complex can stabilize an α-positive charge,
which can subsequently be trapped with nucleophiles.
OR4 (CO)6Co2 OR4 (CO)6Co2
Co2(CO)8 +
R1 R1 R1
R2 R2 R
R3 R3 R3 2
oxidative Nu
Nu: (CO)6Co2 Nu decomplexation
R1 R1
R2 R2
R3 R3

CO2Me CO2Me CO2Me

N Tf2O, CH2Cl2, N N
MeNO2, -10°C I2
JCSCC 1991, 544
TBSO O O
(OC)6Co2
tBu N tBu
HO
Co2(CO)6

Co2(CO)6-acetylene deocomplexation: JOC 1997, 62, 9380

From Aldehydes and Ketones

R R'
R'-X
P3P, CBr4 Br 2 eq. nBuLi ClCO2Et
R R _ Li+
RCHO R CO2Et
Br H2O

R H
 C≡C BOND FORMATION 117

Br2C a) nBuLi,
OSitBuPh2 THF, -78°C MeO2C
OHC OSitBuPh2 CBr4, Ph3P OSitBuPh2
b) ClCO2Me
OSitBuPh2
OHC OSitBuPh2 OSitBuPh2
Br2C MeO2C
JACS 1992, 114 , 7360

- by conversion of ketones to gem-dihalides followed by elimination

O Cl
PCl5 Cl Cl tBuOK
R' tBuOK
R' R' R R'
R R - HCl R - HCl

- by conversion of ketones to enol phosphates followed by elimination

P(O)(OEt)2 LiNH , NH JOC 1987,
O LDA, (EtO)2P(O)Cl O 2 3
52 , 4885
R R'
R' R'
R R

- Insertion reaction of a vinyl carbene (terminal acetylenes)

N2
O +
••
N2CHP(O)(OMe)2 C -N2 C
R R' JOC 1982,
R R' 47 , 1837
tBuOK R R' R R'

O
Me3Si N2
_
THF, Synlett 1994, 107
-78°C → RT

Via Elimination Reactions of Vinyl Halides

- Treatment of vinyl halides with strong base gives acetylenes.
X
R' Base
R R R'
H - HX

X= Cl, Br, I, OTf, O3SR, OP(O)R2 Base= LDA; tBuOK; NaNH2, DBU

- Addition of Grignard reagents to 1,1-difluoroethylene yields an acetylide anion

which can be subsequently trapped with electrophiles.
H2C=CF2 E+
_ TL 1982, 23 , 4325
R-MgX R R E JOC 1976, 41 , 1487

Strained Rings Topics in Current Chemistry 1983, 109, 189.

- Cyclopropenones and cyclobutendiones can be photolyzed or thermolyzed
(FVP) to give acetylenes.
O O
hν (209 nm) C
- CO - CO JACS 1973,
O 95 , 6134
8 °K
O C
O Benzyne
 C≡C BOND FORMATION 118

1) 370 °C
2) 12°K ACIEE 1988,27 , 398
O
- CO JACS 1991, 113 , 6943

R1
R2
FVP
R1 R2 +
(retro- D-A)

CL 1982, 1241

Eschenmoser Fragmentation
Ph

O N Ph R
N Base
R R -or- HCA 1972,
heat O 55 , 1276
O
R' R' R'

HN NH2
iPr iPr
O O
O tBuOOH,
triton B, C6H6
O iPr JOC 1992, 57, 7052

AcOH, CH2Cl2

Allenes Tetrahedron 1984, 40, 2805

- from dihalocyclopropanes
R Br R R R'
_ H
••

Br Br R H
R' R' R'

- From SN2' Reactions

Nu: X Nu H
R
R' R R'

- from sigmatropic rearrangements from propargyl sulfoxides and phosphine

oxides.
Ph
Ph O
OH Ph2PCl, Et3N :P R' TL 1990, 31 , 2907
O Ph2P JACS 1990, 112 , 7825
R
R' R R H
R'