Alcohol-based Michaelis–Arbuzov reaction: an efficient and environmentally-benign method for C–P(O) bond formation

Abstract

Ann-Bu4NI-catalyzed C–P(O) formation reaction of alcohols with phosphites, phosphonites, and phosphinites is developed for the synthesis of useful phosphoryl compounds.

Dehydrative Synthesis of Functionalized Skipped Dienes from Stabilized Phosphonium Ylides and Allylic Alcohols in Water

“…To our best knowledge, reports on the synthesis of functionalized terminal skipped dienes are still rare. [9] With our continuous interests in alcohol-based alkylation [10] and aqueous media reactions, [11] herein, we wish to report a mild and activator-free dehydrative cross-couplings of stabilized phosphonium ylides with allylic alcohols in water media for the efficient synthesis of functionalized terminal skipped dienes (Scheme 1D). [7] The groups of You and Tian have independently reported the allylic alkylation of phosphonium ylides with allylic esters or amines for the efficient synthesis of terminal functionalized skipped dienes (Scheme 1C).…”

“…The method can also be applied to other common allylic alkylating reagents such as allylic ethers and esters under additive-free conditions. Other protic solvents that were widely used as good hydrogen bond donors, [18] were also investigated, but the target 4 a were obtained only in low to moderate yields, showing that water is an indispensable solvent for the reaction (runs [7][8][9][10][11]. [13] Noteworthy, possibly owing to that water media is theoretically disadvantageous to dehydrative reactions, the activator-free dehydrative couplings of allylic alcohols in water are much rare.…”

“…[8] Possibly owing to the poor leaving character of the hydroxy group, allylic alcohols, more easily-available, cheaper and stable, have not been employed to streamline the synthesis of functionalized terminal skipped dienes. [9] With our continuous interests in alcohol-based alkylation [10] and aqueous media reactions, [11] herein, we wish to report a mild and activator-free dehydrative cross-couplings of stabilized phosphonium ylides with allylic alcohols in water media for the efficient synthesis of functionalized terminal skipped dienes (Scheme 1D). The method can also be applied to other common allylic alkylating reagents such as allylic ethers and esters under additive-free conditions.…”

“…The ligands were also investigated, but dppf is still the best one (runs 5-6). Other protic solvents that were widely used as good hydrogen bond donors, [18] were also investigated, but the target 4 a were obtained only in low to moderate yields, showing that water is an indispensable solvent for the reaction (runs [7][8][9][10][11]. Surprisingly, the reaction under air could also give the target 4 a in 80% isolated yield (run 12).…”

Catalytic Deoxygenative Coupling of Aromatic Esters with Organophosphorus Compounds

“…Diphenyl(thiophen-2-ylmethyl)phosphine oxide (3A) [18] Purification by PTLC (hexane/acetone = 1:3) afforded 3A as a white solid (53.1 mg, 89% yield). 1 (Furan-2-ylmethyl)diphenylphosphine oxide (3C) [19] The reaction was conducted by using 3.0 equiv of 2A.…”