78462-91-6

Upstream product

• 119-61-9 benzophenone 
• 14467-94-8 diethyl <(trimethylsilyl)methyl>phosphonate 
• 13249-58-6 1-bromo-2,2-diphenylethylene 
• 91083-76-0 Ph₂CCHSnBu₃ 
• 591-50-4 iodobenzene 
• 3450-67-7 diethyl phenylethynylphosphonate 
• 25411-73-8 diethyl diazomethylphosphonate 
• 1450-31-3 Thiobenzophenon 
• 530-48-3 1,1-Diphenylethylene 
• 762-04-9 phosphonic acid diethyl ester 
• 71-43-2 benzene 
• 682-30-4 Diethyl vinylphosphonate 
• 108-86-1 bromobenzene 
• 222180-54-3 diethyl [2-phenyl-2-(2-tosylhydrazono)ethyl]phosphonate 

Downstream Products

• 110907-35-2 (2,2-Diphenyl-ethyl)-phosphonic acid diethyl ester 
• 849728-03-6 ethyl hydrogen (2,2-diphenylvinyl)phosphonate 
• 13249-58-6 1-bromo-2,2-diphenylethylene 
• 19997-66-1 1-iodo-2,2-diphenylethylene 

Relevant academic research and scientific papers

Palladium-Catalyzed Remote C?H Phosphonylation of Indoles at the C4 and C6 Positions by a Radical Approach

Palladium-catalyzed direct C?H activation of indole benzenoid moiety has been achieved in the past decade. However, palladium-catalyzed remote C?H activation of indoles is rare. Herein, we report a challenging palladium-catalyzed remote C4-H phosphonylation of indoles by a radical approach. The method provides access to a series of C4-phosphonylated indoles, including tryptophan and tryptophan-containing dipeptides, which are typically inaccessible by direct C4-H activation due to its heavy reliance on C3 directing groups. Notably, unexpected C6-phosphonylated indoles were obtained through blocking of the C4 position. The preliminary mechanistic studies indicated that the reactions may proceed via a C7-palladacycle/remote-activation process. Based on the strategy, examples of remote C4-H difluoromethylation with BrCF2COOEt are also presented, suggesting that the strategy may offer a general blueprint for other cross-couplings.

Phosphonylated thiocarbonyl ylides from the reaction of aromatic thioketones with diethyl diazomethylphosphonates

The reaction of diazomethylphosphonates with aromatic thioketones at -65 °C to room temperature yields 2,5-dihydro-1,3,4-thiadiazole-2-phosphonates, which eliminates N2 to give phosphonylated thiocarbonyl ylides as reactive intermediates. These sulfur-centered 1,3-dipoles undergo typical reactions of thiocarbonyl ylides, i.e., 1,3-dipolar cycloadditions, cyclodimerization, and electrocyclic ring closure, depending on the involved thioketone and, therefore, on the reaction conditions. In the case of the most reactive thiofluorenone, the phsophonylated thiocarbonyl methanide can be intercepted with thiobenzophenone, a phosphonodithioformate, and tetracyanoethylene. In the absence of such reactive dipolarophiles, cyclodimerization occurs to give the corresponding 1,4-dithiane.

Control of hydroboration of 1-alkynylphosphonates, followed by Suzuki coupling provides regio- and stereospecific synthesis of di-substituted 1-alkenylphosphonates

Hydroboration of 1-alkynylphosphonates can be controlled to place boron on either C1 or C2 of the triple bond by control of reaction conditions. Initial hydroboration occurs on C1 (kinetic product), which can be isomerized to place boron on C2 (thermodyna

Palladium-Catalyzed Olefination of N-Tosylhydrazones as β-Diazo Phosphonate Precursors with Arylhalides

An efficient palladium-catalyzed olefination of N-tosylhydrazones as β-diazo phosphonate precursors with aryl halides has been developed. 2,2-Disubstituted vinylphosphonates bearing versatile functional groups were easily accessed in moderate to excellent

Visible photocatalysis of novel oxime phosphonates: Synthesis of β-aminophosphonates

A novel type of oxime phosphonate was synthesized and used in the intermolecular cascade radical addition reaction of alkenes to access β-aminophosphonates via visible-light-driven N-centered iminyl radical-mediated and redox-neutral selective C-P single-bond cleavage in an active phosphorus radical route. The procedure is characterized by its ability to achieve the construction of Csp3-P and Csp3-N bonds without the requirement for oxidants and bases.

Silver-promoted cascade radical cyclization of γ,δ-unsaturated oxime esters with P(O)H compounds: synthesis of phosphorylated pyrrolines

A cascade radical cyclization was realized for the first silver-promoted imino-phosphorylation of γ,δ-unsaturated oxime esters, which provided a step-economical and redox-neutral route to access a variety of phosphorylated pyrrolines in good to excellent yields. Moreover, a new bulky trivalent phosphine ligand with a pyrroline motif was obtained through a deoxidation process.

TEMPO and Silver-Mediated Intermolecular Phosphonylation of Alkenes: Stereoselective Synthesis of (E)-Alkenylphosphonates

An efficient method was developed towards the synthesis of alkenylphosphonates from simple olefins and phosphonate diesters. This method was enabled by the use of cheap and commercially available silver salts and TEMPO. This method exhibits of good functional group tolerance, specific (E)-selectivity for all olefins and vinyl selectivity for aliphatic olefins. A radical mechanism was proposed, and TEMPO was involved in the product formation step.

Visible-Light-Catalyzed Phosphonation-Annulation: an Efficient Strategy to Synthesize β-Phosphonopyrrolidines and β-Phosphonolactones

A new type of phosphine radical precursor for C—P bond formation has been developed and successfully used in visible-light-catalyzed phosphonation-annulation of unsaturated sulfonamides and carboxylic acids. The catalytic process is simple and green acces

Mono and double Mizoroki-Heck reaction of aryl halides with dialkyl vinylphosphonates using a reusable palladium catalyst under aqueous medium

Operationally-simple and reusable Pd-catalyzed mono and double Mizoroki-Heck reactions of aryl halides and dialkyl vinylphosphonates using iPr2NH as a base in aqueous medium under air were developed. For aryl iodides, the reaction could be conducted at 80 °C under a low catalyst loading (0.1-1 mol%). When aryl bromides were applied, however, a greater amount of catalyst (5 mol%) and a longer reaction time at 120 °C were required. Simply changing dialkyl vinylphosphonates as the limiting reagent led to the formation of 2,2-diaryl vinylphosphonates in good to high yields. After reaction, the residual aqueous solution could be reused for both mono and double Mizoroki-Heck reactions, making the reactions greener and reducing wastage of precious metals and use of harmful organic solvents as the reaction medium.

Mn(OAc)3-Promoted Oxidative Csp3-P Bond Formation through Csp2-Csp2 and P-H Bond Cleavage: Access to β-Ketophosphonates

The Mn(OAc)3-promoted oxidative phosphonylation of N,N-dimethylenaminones with H-phosphonates, involving a chemo- and regioselective Csp2-Csp2 bond cleavage and Csp3-P bond formation in one step, provided successfully functionalized β-ketophosphonates under mild reaction conditions. Oxidative Csp3-H/P-H cross-coupling reactions via Csp3-C(C=O) bond cleavage and mechanistic studies are conducted preliminarily, and a possible mechanism is proposed. This novel method proceeds in good to excellent yields, shows operational simplicity, broad substrate scope, and large-scale preparation.