Phosphines, naming

The reaction of larger phosphines, namely P( Pr)3, with [(=SiO)Rh(allyl)2L] is noteworthy (Scheme 58). 

NaaCOs, affords high yields in the reaction of 4-chloroanisole (71) with -butyl acrylate (38) in DMA at 140 °C. This is likely to be the highest temperature that has appeared in literature for hgand-accelerated Mizoroki-Heck reactions of unreactive aryl chlorides. In the same protocol, several bulky secondary phosphines, namely bis(adamantyl)phosphine, bis(norbomyl)phosphine and f-BuaPH, were also operative yet inferior to f-BusP [133]. Unlike the Hartwig-Fu protocol, this method has found no application so far, which is why its scope cannot be reliably assessed. 

The menthyl group has also been widely used in the preparation of P-stereogenic small ring heterocyclic phosphines, namely phosphiranes and phosphetanes. ... 

The first example of a triphosphine combining a carbon, a phosphorus and a plane as stereogenic elements was reported by Barbaro, Giambastiani and co-workers. " The synthesis of this phosphine, named P3Chir, starts with the commercially available phosphine PPFA (Scheme 2.47). 

Volatile hydrides, except those of Periodic Group VII and of oxygen and nitrogen, are named by citing the root name of the element (penultimate consonant and Latin affixes. Sec. 3.1.2.2) followed by the suffix -ane. Exceptions are water, ammonia, hydrazine, phosphine, arsine, stibine, and bismuthine. 

Some compounds are named as derivatives of the simple phosphoms hydrides (phosphines). For example, dimethylphosphine [676-59-5], (CH2)3PH triphenylphosphine oxide [791-28-6], (CgH3)3P=0 1,2-dimethyldiphosphine [53684-00-7], CH PHPHCH diethyliodophosphine [20472-47-3], (C2H3)2PI phosphonium iodide [12125-09-6], PH" P tetramethylphosphonium chloride [1941 -19-1], (CH3) P" C1 and phenylphosphonium bromide [55671-96-0], CgH PHjBr-. 

Ethyl (triphenylphosphoranylidene)acetate is available from FIuka AG and Trldom Chemical Inc. under the name (ethoxycarbonylmethylene)triphenyl-phosphorane and from Aldrich Chemical Company, Inc. under the name (carbethoxymethylene)triphenylphosphorane. The reagent may be prepared from triphenyl phosphine and ethyl bromoacetate by the following procedure. ... 

The recommended names for these compounds (phosphinic acid and phosphinates) have not yet gained wide acceptance for inorganic compounds but are generally used for organophosphorus derivatives. Hypophosphites can be made by healing white phosphorus in aqueous alkali ... 

Divalent sulfur compounds are achiral, but trivalent sulfur compounds called sulfonium stilts (R3S+) can be chiral. Like phosphines, sulfonium salts undergo relatively slow inversion, so chiral sulfonium salts are configurationally stable and can be isolated. The best known example is the coenzyme 5-adenosylmethionine, the so-called biological methyl donor, which is involved in many metabolic pathways as a source of CH3 groups. (The S" in the name S-adenosylmethionine stands for sulfur and means that the adeno-syl group is attached to the sulfur atom of methionine.) The molecule has S stereochemistry at sulfur ana is configurationally stable for several days at room temperature. Jts R enantiomer is also known but has no biological activity. 

Esters of phosphinic acid, H2P(0)(0H), are named by the same methods as used for phosphonates. For examples with two P-C bonds see 2-Carb-31.3. 

Note. Names based on phosphane, rather than phosphine or phosphorane, are used in this document, as recommended in [14]. 

Tervalent organophosphorus compounds containing one single P-N bond with the valency of each atom saturated by protons or carbons (but no other heteroatoms) have been known since their discovery by MichaeUs more than one century ago [ 1 ] and named indistinctly as aminophosphanes, phosphanamines, phosphazanes, or phosphinous amides. This last chemical nomenclature is the one used by the Chemical Abstracts Service (CAS) for indexing these compounds and is also the one that best delimits the scope of this review those species derived from the parent H2P-NH2 (phosphinous amide in CAS nomenclature) by partial or total substitution of protons by hydrocarbon radicals (Table 1). 

This chapter will also deal with compounds containing two or three phosphinous amide units, which, for simpUcity, will be named here as bis(amino-phosphanes) or tris(aminophosphanes) but not with phosphinous amides containing other additional organophosphorus functionaUties as, for instance, the so-called aminophosphine phosphinites (AMMP), which have been the subject of increasing attention in the Uterature dealing with catalytic asymmetric transformations and have been treated in other reviews [2,3]. 

However, when each diastereomerically pure l-acetoxy-//-phosphinate 80 was subjected to enzymatic hydrolysis, only one of them, namely (R, Sp)-80, underwent the desired reaction, the other one, (R, Rp)-80, being totally unreactive (Scheme 7). ... 

Among electron-rich chiral phosphines, chiral phospholanes have emerged to be one of the most efficient classes of ligands in metal catalyzed enantioselective reactions. We have developed a novel family of bisphospholane ligand namely, catASium M, from laboratory to commercial scale. Trimethylsilylphospholane 1 was employed as a key intermediate to provide access to a large variety of ligands. 

A reaction of the first type, in a broad sense, uses the mixture obtained from n-BuLi and the phosphinic acid (mes)2P(H)=0 (mes = 2,4,6-trimethylphenyl) in thf/hexane to which the Cd amide Cd[N(SiMe3)2]2 is added a mixed amide-phosphinite is obtained, namely [ MeSi)2N Cd (mes)2PO 2Li-2 thf]. The structure analysis (153 K) reveals that the two phosphinite ligands act as a double bridge between Cd and Li to give a six-membered, twisted ring with two independent Cd—P bonds (rav(Cd—P) 259.4 pm) the exocyclic Cd—N bond is rather short (213.6 pm).226... 

A new class of metaphosphinates, namely iminomethylenephosphoranes (1 with R = N(SiMe3)2, X = NSiMe3) is accessible by reaction of diazoalkanes with imino-phosphines (SiMe3)2N—P=N—SiMe3. Depending on the substituents on the methylene carbon atom, compounds of this class are either stable or dimerize across the P=C or P=N double bond 141). 

Functionally substituted phosphines play an important role as ligands in a great variety of phosphorus coordination compounds. They have some interesting features that distinguish them from other phosphine ligands, namely (a) the presence of other heteroatoms bearing lone electron pairs in addition to phosphorus (b) the presence of functional groups able to form bonds with a metal with the participation of its valence electrons ... 

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