Novel addition reactions of titanacycle phosphonates by tuning of Ti(O-i-Pr)4/2i-PrMgClElectronic supplementary information (ESI): further experimental details. See http://www.rsc.org/suppdata/cc/b2/b209149f/

Abstract

Di-or tri-substituted vinylphosphonates, 2-5, can be obtained in a highly regio-and stereoselective manner from 1-alkynylphosphonates, by manipulation of Ti(O-i-Pr) 4 /2i-PrMgCl. † Electronic supplementary information (ESI): further experimental details. See

Regio- and Stereoselective Hydrophosphorylation of Ynamides for the Synthesis of β-Aminovinylphosphine Oxides

“…Vinylphosphorus compounds are versatile building blocks in synthetic, materials, and medicinal chemistry because of their unique structural features and biological activities . Over the past decades, various synthetic methods for vinylphosphorus compounds have been developed, including a transition-metal-catalyzed cross-coupling reaction of prefunctionalized alkenes, metal-promoted hydrophosphorylation reaction of alkynes, addition reaction of alkynylphosphorus compounds, phosphorus addition of allenes, and radical cyclization of alkynoates (Scheme ). Among them, the hydrophosphorylation reaction of alkynes has emerged as a straightforward method with easy access to diverse alkyne substrates.…”

Synthesis of Dihydrothiophene, Thiophene, and Their Selenium Analogues Carrying Four Phosphoryl Groups

“…Although a cyclopentadienyl ligand with five phosphorus substituents has been synthesized recently, the introduction of the phosphorus substituents onto a benzene ring is still limited to four substituents . On the other hand, phosphoryl acetylenes have been reported as convenient synthetic intermediates or building blocks for phosphoryl compounds and can undergo various reactions such as [2 + 2], [3 + 2], and [4 + 2] cycloadditions, conjugate additions, and metallacycle formation . Recently, we have been involved in constructing cyclic π-conjugated systems substituted with phosphorus functional groups, and we have employed diphosphorylacetylenes for the synthesis of the η 4 -(tetraphosphorylcyclobutadiene)cobalt complexes, which work as bisbidentate ligands to form a one-dimensional coordination polymer .…”

Novel One-Pot Synthesis of 3-Amino-1-alkenylphophonates by Addition of Imines to Alkynylphosphonate Titanium(II) Complexes

“…Another method involves a seven-stage process starting from Michael addition of dimethyl methylphosphonate to 4-chloro-β-nitrostyrene and catalytic reduction of the nitro group, followed by hydrolysis of the resulting amine ) . The in situ-generated divalent titanium complex was initially discovered by Kulinkovich .…”