Chemoselective reduction of the phosphoryl bond of O-alkyl phosphinates and related compounds: an apparently impossible transformation.
نویسندگان
چکیده
A method is reported for the phosphoryl bond cleavage of O-alkyl phosphinates, phosphinothioates and certain phosphonamidates to furnish the corresponding P(III) borane adducts. The two-step procedure relies upon initial activation of the phosphoryl bond with an alkyl triflate, followed by reduction of the resulting intermediate using lithium borohydride.
منابع مشابه
Origin of Catalytic Activity Differences between Phosphine and Phosphine Oxide-Based Structures in the Water-Crosslinkable Polyalkoxysilane Composition
Organocatalysts have attracted enormous interest in the water-crosslinking reaction in silane-grafted polyolefins (SGPOs) system owing to their simplicity, low toxicity and environmentally benign nature compared to organotin catalysts, which are most used in SGPOs system. We focus on organophosphorus compounds including four structure types as organocatalysts; phosphoric acids, phosphoric ester...
متن کاملMECHANISMS OF PREDICTION AND POTENTIAL CAUSATION OF ORGANOPHOSPHATE INDUCED DELAYED NEUROTOXICITY by Nichole
Serine esterases are inhibited by dialkyl fluorinated aminophosphonate (FAP) compounds of general formula, (RO)2P(O)C(CF3)2NHS(O)2C6H5, where R = alkyl. It has been hypothesized that the active site serine of the esterase covalently attaches to the phosphoryl moiety of the FAP compound, resulting in formation of a dialkyl phosphate adduct that can age by net loss of an R-group. However, this me...
متن کاملCleavage of P=O in the presence of P-N: aminophosphine oxide reduction with in situ boronation of the P(III) product.
In contrast to tertiary phosphine oxides, the deoxygenation of aminophosphine oxides is effectively impossible due to the need to break the immensely strong and inert PO bond in the presence of a relatively weak and more reactive PN bond. This long-standing problem in organophosphorus synthesis is solved by use of oxalyl chloride, which chemoselectively cleaves the PO bond forming a chloroph...
متن کاملThe Chemoselective Reduction of Isoxazoline γ-Lactams Through Iminium Aza-Diels-Alder Reactions: A Short-Cut Synthesis of Aminols as Valuable Intermediates towards Nucleoside Derivatives
Isoxazoline γ-lactams are prepared starting from the regioisomeric cycloadducts of benzonitrile oxide to the N-alkyl 2-azanorbornenes taking advantage of the efficient catalytic oxidation by RuO(4). The reduction of the amide groups is easily conducted in the presence of LiAlH(4) under mild conditions, which allowed for the chemoselective reduction of the amide moiety followed by ring opening t...
متن کاملA chemoselective and green reduction of nitro arenes to aromatic amines with FeSO4, NaBH4, H3PW12O40 in water at room temperature
A new efficient and practical method for the room-temperature reduction of aromatic nitro compounds employing FeSO4. 7H2O, NaBH4, H3PW12O40 system in H2O under mild conditions is reported. The method is simple, inexpensive, easily scaled-up and applicable for the large scale preparation of different substituted anilines.
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Chemical communications
دوره 51 92 شماره
صفحات -
تاریخ انتشار 2015