SYNTHESIS AND PROPERTIES OF COMPOUNDS RELATED TO 1-t-BUTYLACETYLENE-2-PHOSPHONIC ACID AND 1-t-BUTYLETHANE-1,2,2-TRIPHOSPHONIC ACID. STERICALLY OVERCROWDED PHOSPHORUS COMPOUNDS, PART I:

Facile Synthesis and Self‐Assembly of Zinc (2‐Diethoxyphosphorylethynyl)porphyrins

“…Alkynylphosphonates are widely studied compounds, but traditional synthetic approaches to these compounds suffer from several drawbacks such as the use of air‐ and moisture‐sensitive chemicals and lack of functional group tolerance , , . Therefore, alternative strategies have been developed in the recent years, most of which being based on transition metal‐catalyzed reactions, in the first place the cross‐coupling reactions of acetylenes with electrophilic[3d], , or nucleophilic[10h], , phosphorus derivatives. Palladium‐ or rhodium‐catalyzed functionalization of aryl halides by phosphorus‐substituted acetylenes has also been explored, but not so extensively as the other cross‐coupling methods.…”

Dialkyl 1-Alkynylphosphonates: a Range of Promising Reagents

“…[23,27] In 1990, two innovations worthy of merit were reported. [28,29] The first featured alkynylphenyliodonium salts [28] as alkynylating agents and the second featured NiCl 2 as a catalyst. [29] Alkynylphenyliodonium tosylates 11 react with trialkyl phosphites 1 in a formal Michaelis-Arbuzov reaction to give dialkyl 1-alkynylphosphonates 3 (Scheme 5).…”

“…[28,29] The first featured alkynylphenyliodonium salts [28] as alkynylating agents, while the second featured NiCl 2 as a catalyst. [29] Alkynylphenyliodonium tosylates 11 react with trialkyl phosphites 1 in a formal MichaelisϪArbuzov reaction to give dialkyl 1-alkynylphosphonates 3 (Scheme 5). It seems plausible that the first step in this reaction is a Michael addition of the trimethyl phosphite 1 (R ϭ Me) to the electron-deficient β-carbon to form an ylide, which undergoes loss of iodobenzene and formation of vinylidene.…”

“…[28] At the same time, it was reported that 1-tert-butyl-2-chloroacetylene reacts with trialkyl phosphites 1 between 110 and 160°C in the presence of a catalytic amount of anhydrous NiCl 2 to give the corresponding alkynyl esters in good yields: 73% for the ethyl ester and 75% for the isopropyl ester. [29] …”

“…[111] For example, 1-tert-butylacetylenephosphonate is subject to nucleophilic attack by the sodium diethyl phosphite 12 (in THF at room temperature for 24 h) to give a triphosphonate in good yield. [29] A decrease in the activity of sodium diethyl phosphite 12 was observed in ethanolic solutions. The triple bond is attacked by the sodium diethyl phosphite 12 at the β-position with respect to the bulky group, rather than β to the phosphoryl group, steric hindrance predominating over the electronic directing influence of the phosphoryl group.…”