Alkynes Alkynylation

REACTIONS OF OsH2(T)2-H2)(CO)(P Pr3)2 WITH ALKYNES ALKYNYL AND RELATED COMPOUNDS... 

The transition metal-catalysed coupling reaction of aryl halides with alkynes (alkynylation of aryl halides) is frequently also considered as a Heck reaction [68, 108-111], Polymers containing arylacetylene and diarylacetylene units in the backbone have been obtained by the self-coupling of ethynylaryl halides [scheme (3)] and the cross-coupling of aromatic dihalides with acetylene [scheme (6)] or diethynylbenzenes [scheme (7)] [112-121]. The majority of... 

Addition of terminal alkynes to [RhCl(PPr )2]n affords a range of interconvertible alkyne, alkynyl and vinylidene species which are described in the carbene section of this review. The NMR spectra of [RhH(CsCPh)(X)(PPh3)2L] [X = Cl, OCN, N3, CsCPh L = NCsH2-3,4-(C02Me)2-4-Ph] have been reported.276... 

The reaction of [RhCl(PPr 3)2]n with Mc3SiCsCC CSiMe3 afforded structurally characterised trans-[RhCl(Ti2-Me3SiCaCOCSiMe3)(PPr 3)2] in which one of the CX triple bonds is uncoordinated. The reaction of [RhCl(PPr 3)2]n with y-functionalised alkynes HGCCRR X (X = OH, OMe, Cl, NH2) afforded either alkyne, alkynyl(hydrido) or vinylidene rhodium complexes depending on the nature of the substituents. 

In principle, calculations such as these may be benchmarked against experimental studies where the kinetics of the conversion between the alkyne, alkynyl... 

The alkynyl iodide 359 undergoes cross-coupling with a terminal alkyne to give the 1,3-diyne 360[264]. No homocoupling product is formed. This reaction offers a good synthetic method for unsymmetrical 1,3-diynes. 

The carbonylation of aryl iodides in the presence of terminal alkynes affords the acyl alkynes 565. Bidentate ligands such as dppf give good results. When PhjP is used, phenylacetylene is converted into diphenylacetylene as a main product[4l5]. Triflates react similarly to give the alkynyl ketones 566[4I6], In... 

The alkynyl ketones 840 can be prepared by the reaction of acyi chlorides with terminal alkynes, Cul in the presence of Et3N is the cocatalyst[719]. (1-Alkynyl)tributylstannanes are also used for the alkynyl ketone synthesis[720]. The a,. 3-alkynic dithio and thiono esters 842 can be prepared by the reaction of the corresponding acid chloride 841 with terminal alkynes[721,722]. 

The 2,3-alkadienyl acetate 851 reacts with terminal alkynes to give the 2-alkynyl-1,3-diene derivative 852 without using Cul and a base. In the absence of other reactants, the terminal alkyne 853 is formed by an unusual elimination as an intermediate, which reacts further with 851 to give the dimer 854. Hydrogenolysis of 851 with formic acid affords the 2, 4-diene 855[524]. 

Propargylic (or 2-alkynyl) compounds are derivatives of alkynes. However, Pd-catalyzed reactions of propargylic derivatives, particularly esters and halides, are very different mechanistically from those of simple alkynes, except in a few cases. Therefore, the reactions of propargylic esters and halides are treated in this section separately from those of other alkynes. However, some reactions of propargylic alcohols, which behave similarly to simple alkynes, are treated in Section 6. 

Terminal alkynes react with propargylic carbonates at room temperature to afford the alka-l, 2-dien-4-yne 14 (allenylalkyne) in good yield with catalysis by Pd(0) and Cul[5], The reaction can be explained by the transmetallation of the (7-allenylpailadium methoxide 4 with copper acetylides to form the allenyKalk-ynyl)palladium 13, which undergoes reductive elimination to form the allenyl alkyne 14. In addition to propargylic carbonates, propargylic chlorides and acetates (in the presence of ZnCb) also react with terminal alkynes to afford allenylalkynes[6], Allenylalkynes are prepared by the reaction of the alkynyl-oxiranes 15 with zinc acetylides[7]. 

In addition to alcohols, some other nucleophiles such as amines and carbon nucleophiles can be used to trap the acylpalladium intermediates. The o-viny-lidene-/j-lactam 30 is prepared by the carbonylation of the 4-benzylamino-2-alkynyl methyl carbonate derivative 29[16]. The reaction proceeds using TMPP, a cyclic phosphite, as a ligand. When the amino group is protected as the p-toluenesulfonamide, the reaction proceeds in the presence of potassium carbonate, and the f>-alkynyl-/J-lactam 31 is obtained by the isomerization of the allenyl (vinylidene) group to the less strained alkyne. 

Alkyl- and aryl-pyridazines can be prepared by cross-coupling reactions between chloropyridazines and Grignard reagents in the presence of nickel-phosphine complexes as catalysts. Dichloro[l,2-bis(diphenylphosphino)propane]nickel is used for alkylation and dichloro[l,2-bis(diphenylphosphino)ethane]nickel for arylation (78CPB2550). 3-Alkynyl-pyridazines and their A-oxides are prepared from 3-chloropyridazines and their A-oxides and alkynes using a Pd(PPh3)Cl2-Cu complex and triethylamine (78H(9)1397). 

The alkynylation of estrone methyl ether with the lithium, sodium and potassium derivatives of propargyl alcohol, 3-butyn-l-ol, and propargyl aldehyde diethyl acetal in pyridine and dioxane has been studied by Miller. Every combination of alkali metal and alkyne tried, but one, gives the 17a-alkylated products (65a), (65c) and (65d). The exception is alkynylation with the potassium derivative of propargyl aldehyde diethyl acetal in pyridine at room temperature, which produces a mixture of epimeric 17-(3, 3 -diethoxy-T-propynyl) derivatives. The rate of alkynylation of estrone methyl ether depends on the structure of the alkyne and proceeds in the order propar-gylaldehyde diethyl acetal > 3-butyn-l-ol > propargyl alcohol. The reactivity of the alkali metal salts is in the order potassium > sodium > lithium. 

Allylation of perfluoroalkyl halides with allylsilanes is catalyzed by iron or ruthenium carbonyl complexes [77S] (equation 119) Alkenyl-, allyl-, and alkynyl-stannanes react with perfluoroalkyl iodides 111 the presence ot a palladium complex to give alkenes and alkynes bearing perfluoroalkyl groups [139] (equation 120)... 

Chemoselective alkynylation in the C-3 position of N-substituted 3,5-dichloropyrazin-2(lH)-one has been described by Van der Fycken et al. [27]. When a mixture of 3,5-dichloro-l-benzylpyrazin-2(lH)-one and pheny-lacetylene in a mixture of NFts and DMF, using Pd(OAc)2/PPh3 as precatalyst and Cul as a co-catalyst, was irradiated for 15 min at 120 °C, the desired l-benzyl-5-chloro-3-phenylethynylpyrazin-2(lH)-one could be isolated with a 77% yield (Scheme 50). Although 2.4 equiv of alkyne were used, no trace of the 1-benzyl-3,5-diphenylethynylpyrazin-2(lH)-one could be detected. 

---