Organoborane or organoboron compounds are chemical compounds of boron and carbon that
are organic derivatives of BH3, for example trialkyl boranes.
Organoboron chemistry or organoborane chemistry is the chemistry of these compounds.
Organoboron compounds are important reagents in organic chemistry enabling many chemical
transformations, the most important one called hydroboration.
== Properties of the B-C bond == The C-B bond has low polarity (the difference
in electronegativity 2.55 for carbon and 2.04 for boron), and therefore alkyl boron compounds
are in general stable though easily oxidized.
In part because its lower electronegativity, boron often forms electron-deficient compounds,
such as the triorganoboranes.
Vinyl groups and aryl groups donate electrons and make boron less electrophilic and the
C-B bond gains some double bond character.
Like the parent borane, diborane, organoboranes are classified in organic chemistry as strong
electrophiles because boron is unable to gain a full octet of electrons.
Unlike diborane however, most organoboranes do not form dimers.
== Synthesis ==
=== From Grignard reagents ===
Simple organoboranes such as triethylborane or tris(pentafluorophenyl)boron can be prepared
from trifluoroborane (as the ether complex) and the ethyl or pentafluorophenyl Grignard
reagent.
=== From alkenes === Boranes react rapidly to alkenes in a process
called hydroboration.
This concept was discovered by Dr. Herbert Charles Brown, work for which he eventually
received the Nobel Prize (jointly with Georg Wittig for his discovery of the Wittig reaction).
Although diborane as a pure compound is a dimer, BH3 forms 1:1 complexes with basic
solvents, for instance THF.
In an ordinary electrophilic addition reaction of HX (X = Cl, Br, I, etc.), Markovnikov's
rule, which states that the less electronegative atom, usually hydrogen, adds to the least
substituted carbon of the double bond, this determines regioselectivity.
With boranes the mode of action is the same, the hydrogen adds to the most substituted
carbon because boron is less electronegative than hydrogen.
When a positive charge develops in the alkene on the most substituted carbon atom, that
is where the partially negatively charged hydrogen atom adds, leaving the least substituted
carbon atom for the boron atom.
The so-called anti-Markovnikov addition because when the boron is replaced with a hydroxyl
group the overall reaction is addition of water over the double bond in what appears
to be an anti-Makovnikov addition.
This is most pronounced when the boron compound has very bulky substituents.
One organoboron reagent that is often employed in synthesis is 9-BBN which is generated from
the reaction of cyclooctadiene and diborane.
Hydroborations take place stereospecifically in a syn mode, that is on the same face of
the alkene.
In this concerted reaction the transition state is represented as a square with the
corners occupied by carbon, carbon, hydrogen and boron with maximum overlap between the
two olefin p-orbitals and the empty boron orbital.
=== By borylation ===
Metal-catalyzed C-H Borylation reactions are transition metal catalyzed organic reactions
that produce an organoboron compound through functionalization of aliphatic and aromatic
C-H bonds.
A common reagent in this type of reaction is bis(pinacolato)diboron.
== Reactions ==
=== Hydroboration-oxidation ===
In organic synthesis the hydroboration reaction is taken further to generate other functional
groups in the place of the boron group.
The hydroboration-oxidation reaction offers a route to alcohols by oxidation of the borane
with hydrogen peroxide or to the carbonyl group with the stronger oxidizing agent chromium
oxide.
=== Rearrangements === A second group of reactions that organoboron
compounds are involved in create new carbon carbon bonds.
Carbon monoxide is found to react very easily with a trialkylborane.
What follows is a 1,2-rearrangement when an alkyl substituent on the anionic boron migrates
to the adjacent electrophilic carbon of the carbonyl group.
The carbonyl group can then be reduced to a hydroxyl group.
=== Allylboration === Asymmetric allylboration demonstrates another
useful application of organoboranes in carbon–carbon bond formation.
In this example from Nicolaou's synthesis of the epothilones, asymmetric allylboration
(using an allylborane derived from chiral alpha-pinene) is used in conjunction with
TBS protection and ozonolysis.
Overall, this provides a two-carbon homologation sequence that delivers the required acetogenin
sequence.
=== As reducing agent === Borane hydrides such as 9-BBN and L-selectride
(lithium tri-sec-butylborohydride) are reducing agents.
An example of an asymmetric catalyst for carbonyl reductions is the CBS catalyst.
This catalyst is also based on boron, the purpose of which is coordination to the carbonyl
oxygen atom.
=== Borates === Trialkylboranes, BR3, can be oxidized to the
corresponding borates, B(OR)3.
One method for the determination of the amount of C-B bonds in a compound is by oxidation
of R3B with trimethylamine oxide (Me3NO) to B(OR)3.
The trimethylamine (Me3N) formed can then be titrated.
Boronic acids RB(OH)2 react with potassium bifluoride K[HF2] to form trifluoroborate
salts K[RBF3] which are precursors to nucleophilic alkyl and aryl boron difluorides, ArBF2.
The salts are more stable than the boronic acids themselves and used for instance in
alkylation of certain aldehydes:
=== Suzuki reaction and related reactions ===
Organoboron compounds also lend themselves to transmetalation reactions, especially with
organopalladium compounds.
This reaction type is exemplified in the Suzuki reaction, which involves coupling of aryl-
or vinyl-boronic acid with an aryl- or vinyl-halide catalyzed by a palladium(0) complex,
This reaction is an important method for making carbon-carbon bonds.
== Classes of organoboron compounds ==
=== Triorganoboranes and hydrides === Among the most studied classes of organoboron
compounds have the formula BRnH3−n.
As discussed above, these compounds are used as catalysts, reagents, and synthetic intermediates.
The trialkyl and triaryl derivatives feature trigonal planar boron center that is typically
only weakly Lewis acidic.
Except for very bulky derivatives, the hydrides exist as dimers, reminiscent of the structure
of diborane itself.
=== Borinic and boronic acids and esters (BRn(OR)3-n) ===
Compounds of the type BRn(OR)3-n are called borinic esters (n = 2), boronic esters (n
= 1), and borates (n = 0).
Boronic acids are used in Suzuki reaction.
Trimethyl borate, which is debatably not an organoboron compound, is an intermediate in
the production of sodium borohydride.
=== Carboranes === Carboranes are cluster compounds with carbon
and boron vertices.
The best known is orthocarborane, with the formula C2B10H12.
Although they have few commercial applications, carboranes have attracted much attention as
precursors to reagents and new materials.
Anionic derivatives, dicarbollides, e.g., [C2B9H11]2− are ligands that behave like
cyclopentadienide.
=== Bora-substituted aromatic compounds === In borabenzene, one CH center in benzene is
replaced by boron.
These compounds are invariably isolated as adducts, e.g., C5H5B-pyridine.
The cyclic compound borole, a structural analog of pyrrole, has not been isolated, but substituted
derivatives known as boroles are known.
The cyclic compound borepin is aromatic.
=== Boryl compounds === Boryl anions have the formula R2B−.
Nucleophilic anionic boryl compounds have long been elusive but a 2006 study described
a boryllithium compound, which reacts as a nucleophile: Organometallic compounds with
metal to boron bonds, (i.e., M–BR2), are known as boryl complexes.
Related ligands are borylenes (M–B(R)–M).
The absence of lithium boryl compounds is notable because in other period 2 elements
lithium salts are common e.g. lithium fluoride, lithium hydroxide lithium amide and methyllithium.
The gap highlights the very low electronegativity of boron.
Reaction of base with a borohydride R2BH does not result in deprotonation to the boryl anion
R2B− but to formation of the boryl anion R2B−H(base)+.
This reaction product has a complete octet.
Instead the boryl compound is prepared by reductive heterolysis of a boron-bromide bond
by lithium metal.
The new boryl lithium compound is very similar to and isoelectronic with N-heterocyclic carbenes.
It is designed to benefit from aromatic stabilization (6-electron system counting the nitrogen lone
pairs and an empty boron p-orbital, see structure A) and from kinetic stabilization from the
bulky 2,6-diisopropylphenyl groups.
X-ray diffraction confirms sp2 hybridization at boron and its nucleophilic addition reaction
with benzaldehyde gives further proof of the proposed structure.
=== Alkylideneboranes === Alkylideneboranes of the type RB=CRR with
a boron – carbon double bond are rarely encountered.
An example is borabenzene.
The parent compound is HB=CH2 which can be detected at low temperatures.
A fairly stable derivative is CH3B=C(SiMe3)2 but is prone to cyclodimerisation.
=== NHC adducts of boron === NHCs and boranes form stable NHC borane adducts.
Triethylborane adducts can be synthesised directly from the imidazolium salt and lithium
triethylborohydride.
Members of this compound class are investigated for use as reagent or catalyst.
=== Diborenes === Chemical compounds with boron to boron double
bonds are rare.
In 2007 the first neutral diborene (RHB=BHR) was presented by Gregory Robinson of the University
of Georgia.
Each boron atom has a proton attached to it and each boron atom is coordinated to a NHC
carbene.
The parent structure with the additional carbene ligands is diborane(2).
A reported diboryne is based on similar chemistry.
== Other uses == TEB – Triethylborane was used to ignite
the JP-7 fuel of the Pratt & Whitney J58 variable cycle engines powering the Lockheed SR-71
Blackbird.
== Notes