Electrophilic reactions boron compounds

In complete parallel to the discussion in Section 3.5, the conditions for forming a stable 2c->-lc complex or T-bonded compound are intimately related to those for catalyzing the corresponding electrophilic displacement reaction. Thus, the implications of 3c/2e T-bonding go far beyond the chemistry of boron compounds. 

So far wc have used only protic acids to help oxygen atoms to leave, Lewis acids work well too, and the cleavage of aryl alkyl ethers with BBr3 is a good example. Trivalent boron compounds have an empty p orbital so they are very electrophilic and prefer to attack oxygen. The resulting oxonium ion can be attacked by Br in an S 2 reaction. 

The removal of all methyl ethers in 22 is performed by using the Lewis acid BBrs. This trivalent boron compound is very electrophilic and attacks the oxygen atom in aryl methyl ether 40 to give intermediate 41. Then, the resulting oxonium ion 42 is attacked by Br in an Sn2 reaction providing the free phenol 44 after aqueous workup. 

It is significant to note that almost all carbocations have known isoelectronic and isostructural neutral boron analogs. Boron compounds also provide useful models for many types of intermediates (transition states) of electrophilic organic reactions. 

This commoner type of reaction involves the attack of carbon or heteroatom nucleophiles onto carbonyl compounds, by direct or conjugate addition, and onto imines. Because we have just dealt with boranes we shall start with the reaction of allylic boron compounds with such electrophiles. You might strictly not call this nucleophilic attack. 

Probably the best modem method for introduction of OF by electrophilic aromatic substitution is lithiation, reaction with a boronate ester, and oxidation.4 These are the same boron compounds that are used in Suzuki coupling (chapter 18) and are made the same way. In this example, selective mono-lithiation by Br/Li exchange on available tribromoanisole 39 (easily prepared by bromination of anisole or phenol) occurs ortho to the MeO group and reaction of aryl-lithium 39 with trimethyl borate gives the boronic ester 40. Peroxyacids such as peracetic acid are usually used for the final oxidation. 

There has been a wide-ranging review of transmetalation reactions of arenes concentrating on the use of boron-containing compounds. The reaction of arylboronate esters and related compounds with alkyl halides is catalysed by copper(I) formation of an aryl—copper intermediate followed by an 5N2-type reaction with the alkyl electrophile is likely. Palladium complexed with a diimine is an excellent catalyst in the phenylation reaction of Michael acceptors with phenylboronic acid so as to yield products such as (16). The nickel-catalysed reaction of phenylboronic acid with styryl epoxides has been shown to yield a-substituted alcohols such as (17). 

Boron Compounds. KCF3BF3 has been prepared in 85% yield by reaction of trimethoxyborane with TMSCF3 and KF and subsequent treatment of the KCF3B(OMe)3 intermediate with aqueous HR Other trifluoromethyltrialkoxyborate salts were obtained in analogous manner and transformed into trifluoro-methylboronic esters by reaction with suitable electrophiles. ... 

The reaction of 2-bromo-6-lithiopyridine (13) with trialkylboranes gives intermediate boron compounds which are versatile intermediates for the preparation of unsaturated nitriles (Scheme 9). A stereospecific synthesis of dehydronerol utilizes the dianion of 3-methylbut-2-enoic acid as an isoprene functionality (Scheme 10). Lithium dianions from aj8-unsaturated acids generally undergo alkylation reactions at the a-carbon atom. In contrast the dicopper dianions undergo more selective y-alkylation (62—99%) and this ratio is generally higher than with the corresponding esters. A study of various acids and their alkylation with allyl electrophiles showed that allylic electrophiles unsubstituted at the y-carbon react... 

In addition to arylboronic acids, arylboronates have also been successfully used in fluorination reactions (Scheme 7.56) [93]. These boron compounds are attractive substrates since they are typically more robust than other boron species and can often be stored for long periods of time. The catalyst system for this reaction was a copper(I) triflate species along with 2 equiv of silver fluoride. While several sources of electrophilic fluorine generated the aryl fluorides, N-fluoro-2,4,6-trimethylpyridinium hexafluorophosphate was the most effective. The chemistry displayed broad functional group tolerance with the lowest yields obtained with heteroarylboronates. The authors were also able to devise a one-pot borylation-fluorination reaction starting from the parent arene. The arene was converted into an arylboronate through an iridium-catalyzed borylation reaction in the first step of the reaction, while fluorination was achieved during the second step. This is particularly attractive since it facilitates the conversion of unfunctionalized substrates into aryl fluorides. 

Most of the compounds in this class have been prepared from preexisting crown ether units. By far, the most common approach is to use a benzo-substituted crown and an electrophilic condensation polymerization. A patent issued to Takekoshi, Scotia and Webb (General Electric) in 1974 which covered the formation of glyoxal and chloral type copolymers with dibenzo-18-crown-6. The latter were prepared by stirring the crown with an equivalent of chloral in chloroform solution. Boron trifluoride was catalyst in this reaction. The polymer which resulted was obtained in about 95% yield. The reaction is illustrated in Eq. (6.22). 

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