Heterocycles from boranes

Tris(dimethylamino)borane similarly fails to 3deld a trivalent boron heterocycle, but gives the spiro-compound (CLXV). A monocyclic system of type (CLXVI) does arise from diethylaminodiphenylborane, and of type (CLXVII) from phenylboronic acid and its analogues 436). 

Mono- and bicyclic phosphorus heterocycles 199, 200, 202, and 203 were synthesized starting from the bifunctional phosphorylating agent bis(diisopropylamino)ethynyl phosphine 195 via ring-closing enyne metathesis using 4,5-dihydroimidazol-2-ylidene ruthenium benzylidene complex, as a catalyst. Bicyclic phosphorus oxides 199 were obtained in 66-83% yield, whereas phosphorus borane derivative 202 was isolated in 74% yield <2001TL8231>. 

Of all of the elements of the Periodic Table, only neighboring carbon and boron share the properties of self-bonding (catenation) and the support of electron-delocalized structures based upon these catenated frameworks. Carbon catenation, of course, leads to the immense field of organic chemistry. Boron catenation provides the nido-, arachno-, and /i p/io-boranes, which may be considered as the borane equivalents of aliphatic hydrocarbons, and the discrete families of c/oso-borane derivatives which bear a for nal resemblance to the aromatic hydrocarbons, heterocycles, and metallocenes. Aside from these analogies, boron and carbon chemistries are also important to each other through their extravagant ability to mix m ways not available to other element-pairs. Thus, the conflux of boron and carbon chemistries effectively provides an element-pair for exploitation in a variety of novel ways. 

Complexation of the latter at phosphorus with borane, followed by methanolysis of the siloxyether function, gives the related o-hydroxyaryl diazaphospholidines. The cage-like triaminophosphine (109) has been obtained from the reaction of tri(2-pyrrolyl)methane with phosphorus trichloride, in the presence of triethylamine. This compound is stable to methanolysis, hydrolysis, and aerial oxidation at room temperature. Phosphorylation of various 1,2,4-triazoles with halophosphines has given a route to the heterocyclic system (110), and routes to various [2,4,l]benzodiazaphosphinines, e.g., (Ill), have also been developed. ... 

A hydrosilylation approach with the silicon being delivered intramolecularly from an OH group in 106 is also regioselective.18 Catalysis by H2PtCl6 efficiently gave the heterocycle 107 and an oxidation of the C-Si bond (cf. the similar reaction on boranes above) gave one regioisomer of the diol 108. 

ROM has been used to prepare phosphine-containing polymer supports (Scheme 20). Norbornyl-substituted monomer 22 was prepared in two steps from d-bromo-iodobenzene. This was then polymerized with diene 23. It was initially envisioned that it would be necessary to convert the phosphine to the borane adduct in order not to poison the metathesis catalyst. Although protection was needed when using the Grubb s type 1 complex as a catalyst, when employing the more active second-generation complex 24, the free phosphine monomer could be used. This has been attributed to the lower affinity of the active form of the catalyst toward coordination of phosphines due to the presence of the electron-rich heterocyclic carbene ligand. 

The new heterocyclic silane (93) can be prepared from 1,4-dilithio-octa-phenyltetrasilane and dichloro(dimethylamino)borane. It is a white. 

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