40632-91-5

Upstream product

• 814-49-3 diethyl chlorophosphate 
• 37892-71-0 tert-butyllithium 
• 31915-90-9 Z-(2-Chlor-3,3-dimethylbutenyl)phosphonsaeuredichlorid 
• 5469-26-1 1-Bromopinacolon 
• 814-16-4 diethyl (3,3-dimethyl-2-oxobutyl)phosphonate 
• 13601-86-0 1-bromo-3,3-dimethyl-1-butyne 
• 762-04-9 phosphonic acid diethyl ester 
• 2303-76-6 sodium diethyl phosphite 
• 92473-47-7 (3,3-dimethylbutynyl)(phenyl)iodonium tosylate 
• 917-92-0 3,3-Dimethylbut-1-yne 
• 135226-09-4 1-(3,3-dimethylbut-1-yn-1-yl)-1λ³-benzo[d][1,2]iodaoxol-3(1H)-one 
• 122-52-1 triethyl phosphite 
• 16865-61-5 tert-butyl-2-chloro-acetylene 
• 64-17-5 ethanol 

Relevant academic research and scientific papers

Copper-catalyzed one-pot synthesis of alkynylphophonates

Copper is found to be an effective catalyst for the preparation of alkynylphophonates. A novel copper-catalyzed one-pot synthesis of alkynylphophonates from terminal alkynes and dialkyl phosphites is developed which involves the haloalkynes intermediates. This method provides a unique and alternative approach to the well-documented oxidative coupling or arylpropiolic acid strategies.

Mukaiyama reagent-promoted metal-free preparation of alkynyl sulfones and phosphonates under mild conditions

An efficient and mild route for the formation sulfur or phosphor-substituted alkynes was herein demonstrated. The Mukaiyama reagent-mediated transformation started from easily-accessible substrates without carbon-carbon triple bonds, and the reaction proceeded under mild conditions (room temperature) in a one-pot manner, requiring for no transition metal-catalysts. The practical protocol featured for good functional groups tolerance (up to 41 examples) and high efficiency (up to 91% yields) towards alkynyl sulfones and alkynyl phosphonates at low cost.

Rhodium(I)-Catalyzed Azide-Alkyne Cycloaddition (RhAAC) of Internal Alkynylphosphonates with High Regioselectivities under Mild Conditions

A regioselective method to access fully substituted 1,2,3-triazolyl-4-phosphonates from the internal alkynylphosphonates by rhodium(I)-catalyzed azide-alkyne cycloaddition (RhAAC) under mild conditions is reported. This approach is water and air compatible and has a broad substrate scope, good functional group tolerance, high yields and excellent regioselectivities. Fully substituted 1,2,3-triazolyl-4-phosphonates are directly prepared from the internal alkynylphosphonates by RhAAC with high 1,4-regioselectivities. The gram-scale preparation, application to carbohydrate synthesis and the solid-phase synthesis of triazolyl-4-phosphonates are highlights of this method. (Figure presented.).

Base-induced one-pot preparation of N- or P-substituted alkynes

An efficient method for the formation of C(sp)-N or C(sp)-P bonds is described. The facile transformation proceeds under mild conditions (0 or -20 °C) in a one-pot manner, and does not require transition-metal catalysts. The base-induced protocol exhibits good functional group tolerance (up to 44 examples) and high efficiency (up to 94 % yield) towards rare heteroatom-substituted acetylenes (N or P). Furthermore, the proposed mechanism was supported by the isolation of a key intermediate. An efficient method for the formation of C(sp)-N or C(sp)-P bonds is described. The facile transformation proceeds in the absence of any transition-metal catalysts under mild conditions (0 or -20 °C) in a one-pot manner with good functional group compatibility and with high efficiency.

Room temperature alkynylation of H-phosphi(na)tes and secondary phosphine oxides with ethynylbenziodoxolone (EBX) reagents

Highly efficient protocols for the alkynylation of H-phosphi(na)tes and secondary phosphine oxides with silyl, aryl and alkyl ethynyl-benziodoxolone (EBX) reagents are reported. Alkynyl phosphorus compounds were obtained in 69-93% yield without the need for a transition metal catalyst at room temperature under open flask conditions.

Hypervalent iodine in synthesis. XXVII. Alkynylphenyliodonium tosylates as alkynylating reagents: Direct conversion of alkynylphenyliodonium tosylates to dialkyl alkynylphosphonates with sodium dialkylphosphonates

Alkynylphenyliodonium tosylates can easily react with sodium dialkylphosphonates to afford a convenient effective method for the preparation of dialkyl alkynylphosphonates.

One-pot synthesis of 1-alkynylphosphonates

1-Alkynylphosphonates 3 are prepared in a one-pot procedure from diethyl phosphorochloridates 2 and alkynyllithiums 1, which are readily generated by the reaction of 1-alkynes with n-BuLi.

Facile synthesis of 1-alkynylphosphonates

1-Alkynylphosphonates 4 are prepared by the in situ β-elimination of enol phosphates 3, which are readily generated by the reaction of sodium enolate of 2-oxophosphonate with diethyl chlorophosphate.

Alkynyliodonium Salts as Alkynylating Reagents: Direct Conversion of Alkynylphenyliodonium Tosylates to Dialkyl Alkynylphosphonates with Trialkyl Phosphites

The treatment of various alkynyl(phenyl)iodonium tosylates 1 (R = t-Bu, s-Bu, i-Pr, cyclopentyl, Ph, and p-MeC6H4; X(-) = OTs(-)) with neat trimethyl phosphite gave the dimethyl alkynylphosphonates 4a and 4d-h in isolated yields ranging from 34 to 90percent.Similar treatment of 1 (R = t-Bu, X(-) = OTs(-)) with neat triethyl and triisopropyl phosphites gave the diethyl and diisopropyl alkynylphosphonates 4b (81percent) and 4c (58percent).The byproducts of these reactions are alkyl tosylates and iodobenzene.The high yields of iodobenzene, determined by GC analysis for the reactions of 1 (R = s-Bu, p-tolyl; X(-) = OTs(-)) with trimethyl phosphite, indicate that the cleavage of the alkynyl(phenyl)iodonium ions with trialkyl phosphites proceeds with high regioselectivity at the alkynyl ligand.

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:

1-t-Butylacetylene-2-phosphonic acid diethyl and di-isopropyl esters 6a 6b were synthesized via the NiCl2 promoted MICHAELIS-ARBUZOV-type reactions.Ethyl iso-propyl and methyl esters 7a-7c of 1-t-butylethane-1,2,2-triphosphonic acid were obtained by three routes including the "anomalous MICHAELIS-BECKER-type" reaction.In addition the parent triphosphonic acid 7d and an anilinium salt 7e were synthesized.These overcrowded molecules exist at ambient temperature in two different rotameric forms.