Boron halides atomic carbon

Boron substituents in the [l,3,2]diazaborolo[l,5- ]pyridine derivative 109 were studied. This compound was obtained via reduction of its precursor 108 with sodium amalgam (Scheme 27). The bromide attached to the boron atom was further displaced with various halide, hydride, sulfur, and carbon nucleophiles <2001JCD378>. [l,2,5]thiadiazolo[2,3- ]pyridine derivative 110 was deprotected (R = Cbz to R=H) by classical hydrogenolysis <2002AGE3866>. 

The metal halide thus functions in similar manner to the proton and may be considered to be an acidic catalyst (cf. Luder and Zuffanti, 19). The catalyst-olefin complex differs in one significant respect from the product formed by the addition of the proton (or the corresponding acid) to the olefin the halide catalyst is a neutral but electronically deficient molecule and combines with the pi electrons of the double bond to form a coordinate bond between the carbon atom and the aluminum or boron. On the other hand, the addition of the positive proton to the double bond results in the formation of a true (covalent) link between carbon and hydrogen. In other words, the complex, while it contains an electron-deficient (hence, positive) carbon atom, is in itself electronically neutral the product of the addition of a proton to the alkene contains a similar carbon atom but is itself electrically positive. It has been suggested (Whitmore and Meunier, 20) that this difference is related to the fact that metal halide catalysts tend to yield much higher polymers than do the acid (proton) catalysts. 

The pathway followed by the reaction is depicted in Figure B4.1. Methoxide anion adds to the a-haloalkenylborane generated by hydroboration of the haloalkyne, and induces migration of an alkyl group from the boron atom to the alkenyl carbon atom. The migration displaces halide anion from the alkenyl carbon atom and the centre is inverted. Finally protonolysis of the carbon-boron bond by acetic acid releases the (/f)-alkcne. 

Many of the coupling reactions require a base such as OAc" or NEt3 in addition to the palladium. In the Heck reaction, for example, the base is used to effect elimination of hydrogen halide from an intermediate palladium complex, thus regenerating the palladium for use in further catalytic cycles. In the Suzuki reaction, on the other hand, the base binds to the boron atom of the boronic acid which activates the carbon-carbon bond for further reaction. 

Croft explains the results in terms of the acceptor property of the boron atoms. They tend to take an electron pair from a donor molecule to form sp bonds. This is why only halides in lower oxidation states react with boron nitride (e.g., CuCl and SbCls but not Cuds or SbCls) This is different from the case of graphite in which the carbon planes are a source of electrons. The intercalation of aluminum and ferric chlorides is attributed by Croft to bonding by the electron pairs of the nitrogen atoms of boron nitride. It is surprising, however, that boron trifluoride and trichloride, which are particularly good electron acceptors, appear unable to become intercalated. 

Boron. Boron is structurally the most bizarre element in the periodic table. Simple bonding rules that are applicable to the other elements have to be bent considerably in order to accommodate the behavior of boron. Boron should be a metal, but it is a semiconductor with unique structures and anomalous physical properties. Combined with metals it participates in metallic bonding but boron atoms are simultaneously covalently bonded to other boron atoms in the higher metal borides. Similar to carbon it does not form mononuclear ions, its halides are molecules, and its other compounds with nonmetals are solids. 

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