Synthesis of unsymmetric phosphorotrithioates by sequential coupling of 1,1-dichloro-N,N-diethylphosphanamine with thiols and sulfenyl chloride.

Herein, we present the first, one-step, direct synthesis of unsymmetric phosphorotrithioates through a process involving sequential coupling of 1,1-dichloro-N,N-diethylphosphanamine with thiols and sulfenyl chloride. This method showcases excellent functional group tolerance, substrate compatibility, and mild reaction conditions, offering a streamlined approach for the challenging phosphorotrithioate synthesis. Additionally, the applicability of this method can be extended to the synthesis of mixed phosphoroselenodithioates.

Synthesis of mixed phosphorotrithioates via thiol coupling with bis(diisopropylamino)chlorophosphine and sulphenyl chloride.

In this study, we report a novel and efficient one-pot synthesis of mixed phosphorotrithioates under mild conditions at ambient temperature, obviating the requirement for supplementary additives. The method's versatility stems from its utilization of diverse thiols as nucleophilic reactants, 1-chloro-N,N,N',N'-tetraisopropylphosphanediamine [bis(diisopropylamino)chlorophosphine] as the phosphorus precursor, and various sulphenyl chlorides as sources of electrophilic sulfur. Notably, our investigation extends beyond mixed phosphorotrithioates to encompass the synthesis of phosphoroselenodithioates, underscoring the broad applicability of this synthetic protocol.

BF3-Et2O promoted bifunctionalization of aldehydes for the synthesis of arylmethyl substituted organophosphorus compounds.

A simple and efficient protocol for the synthesis of arylmethyl substituted organophosphorus compounds is presented. This method involves the reaction of diphenyl phosphite with aldehydes in the presence of BF3-Et2O. In this method, BF3-Et2O plays a dual role, as it facilitates the generation of both hydrophosphonylated intermediate and phenol from diphenyl phosphite. A significant feature of this approach is its tolerance to the presence of external nucleophiles, such as phenol, aliphatic thiols, indole and 3-methylanisole. The simplicity of the reaction conditions and the high yields achieved make this method promising for applications in areas where phosphonate compounds are of interest.

BF3-Et2O Promoted Heteronucleophilic Addition Reactions for the Synthesis of Unsymmetrical gem-Diarylmethyl Thioethers.

Herein, we present the BF3/BF4- mediated activation of diphenyl phosphite for the formation of thionium ions from aldehydes and thiophenols. These reactive species subsequently undergo reaction with in situ generated phenol, resulting in the synthesis of diarylmethyl thioethers. It was demonstrated that the addition of external phenol in the reaction produced unsymmetrical gem-diarylmethyl thioethers in good yields.

Coupling of 1-Chloro-N,N-diisopropylphosphanamine-Based Reagents with Alcohols and Thiosulfonates: A Precise Construction of O-P(O)-S Bonds.

Herein, we present the first mild, one-step direct synthesis of mixed phosphorothioates through selective generation of O-P(O)-S bonds at rt under additive-free condition. Further, reactions of different model natural products with 1,1-dichloro-N,N-diisopropylphosphanamine helped to present an alternative dimerization strategy. The synthetic utility of the methodology was extended for the synthesis of mixed phosphoroselenoates as well. The potential of the reaction was further demonstrated for the synthesis of mixed phosphorothioate bearing two different alcohols.

Sulfonyl-Promoted Michaelis-Arbuzov-Type Reaction: An Approach to S/Se-P Bonds.

By facilitating the chemical conversion of thiols to thiosulfonates, phosphoramidite/phosphite bearing sp3-hybridized carbon serves as an ideal coupling material to forge new connections at room temperature. In this work, a functional group-induced, additive-free, novel, S-P bond-forming approach is presented. This protocol exhibits good functional group tolerance with wide applications that include phosphorylation of cysteine derivatives, development of a one-pot approach to mixed unsymmetrical thiophosphonates, and extension of the concept to different Se-P bonds. Meticulously, our reaction also generated a S-P bond against cyclic 1,2-dithiane-1-dioxide in a byproduct-free manner. These Michaelis-Arbuzov-type reactions are easy to conduct, work efficiently in a reduced reaction time, and are applicable to gram-scale preparation as well.