Acetylene proton

Since the acetylenic proton is acidic, it often needs to be protected as a trialkylsilyl derivative. It is conveniently deprotected with fluoride ion. 

The acetylenic proton The carbanion now eliminates Cl to give a most odd-looking carbene. Can you see what it is ... 

Acetylenic hydrogens are unusual in that they are more shielded than we would expect for protons bonded to sp hybridized carbon This is because the rr electrons circulate around the triple bond not along it (Figure 13 9a) Therefore the induced magnetic field is parallel to the long axis of the triple bond and shields the acetylenic proton (Figure 13 9b) Acetylenic protons typically have chemical shifts near 8 2 5... 

Long-range coupling between protons more than two carbon atoms apart is sometimes observed when v bonds intervene. An example is found in l-methoxy-l-buten-3-yne. Not only does the acetylenic proton, Ha, couple with the vinylic proton H, it also couples with the vinylic proton Hc, four carbon atoms away. The data are ... 

The limits of the original BIRD-FIMBC sequence and the excellent /ci 1 filter quality of the double tuned G-BIRD element is exemplified in the spectra obtained with the molecule 1,3-butadiynyl (ferf-butyl) diphenyl-silane (Figure 6). This molecule provides a stringent test, since it contains all together aliphatic, aromatic and acetylenic protons, and the corresponding ch coupling constant values vary from 125 to 260 Flz. 

The amide ion (ammonia, pKa = 38) is able to completely remove the acetylenic protons of terminal alkynes (pKa = 25). 

Insertion of the alkyne into the Pd-H bond is the first step in the proposed catalytic cycle (Scheme 8), followed by insertion of the alkene and /3-hydride elimination to yield either the 1,4-diene (Alder-ene) or 1,3-diene product. The results of a deuterium-labeling experiment performed by Trost et al.46 support this mechanism. 1H NMR studies revealed 13% deuterium incorporation in the place of Ha, presumably due to exchange of the acetylenic proton, and 32% deuterium incorporation in the place of Hb (Scheme 9). An alternative Pd(n)-Pd(iv) mechanism involving palladocycle 47 (Scheme 10) has been suggested for Alder-ene processes not involving a hydridopalladium species.47 While the palladium acetate and hydridopalladium acetate systems both lead to comparable products, support for the existence of a unique mechanism for each catalyst is derived from the observation that in some cases the efficacies of the catalysts differ dramatically.46... 

Careful 1H and 13C NMR analyses were carried out for both monomers and polymers in order to prove the chemical structures of the polymers. The H NMR spectra of 50 and 52 are shown in Figure 8. As polymerization proceeded, an acetylenic proton peak at 2.0-2.2 ppm disappeared, while a new vinylic proton peak appeared broadly in the 6.8-7.2 ppm range. Since the new peak is weaker than those for the aromatic biphenyl rings and the two peaks are superimposed, it is hard to separate them clearly. The broad peaks at 2.6 and 3.4 ppm are assignable to the methylene protons and methine proton in the ring, respectively. 

A further piece of evidence to elucidate the catalytic pathway of silylformylation was provided by a pair of deuterium-labeled reactions. The results revealed that the scrambling of hydrogen atoms between a hydrosilane and a terminal acetylene is minimal during the reaction and that the hydrogen atom of the formyl group and the vinylic hydrogen are derived from the hydrosilane and the acetylenic proton, respectively (Eq. 8) [15 bj. 

Exps. 9 and 10 are convincing illustrations of the high lrineiic acidity of the ethynyl proton. In principle, there are four reaction pathways if l-bromo-5-hexyne and a strongly basic reagent are allowed to interact abstraction of the acetylenic proton, Br-metal exchange, displacement of Br by the "nucleophilic" part of the base, and elimination of HBr with formation of HCsC(CH2)2CH=CH2- Only the first process takes place under the conditions of this experiment. The kinetic stability of the intermediate LiOC(CH2)4Br is sufficient to allow for successful functionalizations with a number of reagents. For alkylations with most of the alkyl halides, the polarity of the medium will usually be insufficient. 

However, the -effects in the aliphatic systems are still much smaller than the 1012 rate acceleration observed in the cyclohexyl system. As mentioned earlier, this is due to the unfavourable dihedral angle 9 in the alkene protonations and the angle

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In 1999, Carreira identified Zn(II) as a metal that, like Ag(I) and Cu(I), is capable of effecting the metalation of terminal acetylenes under mild conditions. Thus, treatment of terminal alkynes with Zn(OTf)2 and NEt3 at room temperature led to the formation of zinc alkynylides (Eq. 4). The zinc salt and the amine base work in synergy to weaken the acetylenic proton, with the acetylene undergoing complexation to the Zn(II) center and the base effecting subsequent deprotonation (Fig. 1) [11]. 

According to Appendix 1, the pKA value for an acetylene proton is approximately 25, and the pKA value for a carbonyl-protonated amide is approximately 0. Therefore, the order of protonation is as follows ... 

The global utility of this H-NMR alkyne probe is decreased by the scarcity of terminal alkyne adducts relative to the abundance of internal alkyne adducts. Diphenylacetylene and dimethylacetylenedicarboxylate (DMAC) are two particularly popular alkyne ligands which have no acetylenic proton to monitor. An empirical correlation between alkyne irx donation and, 3C chemical shift for the bound alkyne carbons has been recognized (155) which partially fills this spectroscopic need. A plot of alkyne 13C chemical shifts, which span over 100 ppm (Tables II and III), versus N, the number of electrons donated per alkyne to fulfill the effective atomic number guideline, reveals both the advantages and the limitations... 

Bisalkyne d4 monomers, with N = 3 by symmetry, exhibit proton and carbon chemical shifts at higher fields than those of monoalkynes with N = 4. The proton chemical shift of 10.45 ppm for Mo(PhC=CH)2-(S2CNEt2)2 (52) falls nicely between the four-electron donor Mo(CO)-(PhC=CH)(S2CNEt2)2 case (12.6 ppm) and the two-electron donor (7r-C5H5)2Mo(HC=CH) case [7.68 ppm (Table II)]. Additional data for bisalkyne complexes, including pyrrole-N-carbodithioate derivatives, support a correlation of H chemical shifts with alkyne ttj donation, with three-electron donors typically near 10.0 0.5 ppm. Similar H values are found for cyclopentadienyl bisalkyne complexes with terminal alkyne ligands. Chemical shifts between 8.5 and 10.5 ppm characterize all the neutral and cationic bisalkynes listed in Table V except for [CpMo-(RC=CH)2(MeCN)]+ where one isomer has S near 11 ppm for the acetylenic proton (72). 

Abstraction of an acetylenic proton gives a carbanion that has the lone pair of electrons in the sp hybrid orbital. Electrons in this orbital are close to the nucleus, and there is less charge separation than in carbanions with the lone pair in sp2 or sp3 hybrid orbitals. Ammonia and alcohols are included for comparison note that acetylene can be deprotonated by the amide ( NH2) ion, but not by an alkoxide ion ( OR). 

Very strong bases (such as sodium amide, NaNH2) deprotonate terminal acetylenes to form carbanions called acetylide ions (or alkynide ions). Hydroxide ion and alkoxide ions are not strong enough bases to deprotonate alkynes. Internal alkynes do not have acetylenic protons, so they do not react. 

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