Chemistry of BORON and SILICON

BORON
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Borane has a vacant p orbital.
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its position in group IIIB or 13 of the periodic table.
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Boron has only three electrons in the 2p shell and so typically forms
three conventional two-centre two-electron bonds with other atoms in
a planar structure leaving a vacant 2p orbital.
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The vacant orbital is able to accept a lone pair of electrons from a
Lewis base to give a neutral species or can combine with a
nucleophile to form a negatively charged tetrahedral anion
 Hydroboration
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The addition of boron hydrides to alkenes and alkynes

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Hydroboration is regioselective.
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The boron atom always adds to the end of the alkene
●
The boron always becomes attached to the carbon of the double bond
that is less substituted.
 Hydroboration oxidation

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Bulky substituents improve the selectivity of hydroboration.
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Hydroboration is a syn addition of a borane to an alkene
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Regioselectivity is high: the boron adds to the carbon less able to
support a positive charge
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Oxidation occurs with retention of stereochemistry
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The net result of hydroboration–oxidation is addition of water across
the double bond
●
Carbon–boron bonds can be transformed stereospecifically into C–O,
C–N, or C–C bonds.
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a general reaction with a nucleophile of the type –X–Y where the
nucleophilic atom X can be O, N, or even C, and Y is a leaving
group.
Difference between the Baeyer–Villiger
rearrangement and boron chemistry
Allyl and crotyl boranes react using the
double bond

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Allyl and crotyl boranes react stereospecifically
Boron mediated Aldol reaction
Boron mediated reformatosky
Brown hydroboration
Petasis Reaction
Mechanism
 SILICON
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Silicon is immediately below carbon in the periodic table and the
most obvious similarity is that both elements normally have a valency
of four and both form tetrahedral compounds.
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The most important difference is the strength of the silicon–oxygen σ
bond and the relative weakness of the silicon–silicon bond.

●
Bonds to electronegative elements are generally stronger with silicon
than with carbon
●
Silicon–hydrogen bonds are much weaker than their carbon
counterparts and can be cleaved easily.

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Silicon has a lower electronegativity (1.8) than carbon (2.5) and
therefore C–Si bonds are polarized towards the carbon. This makes
the silicon susceptible to attack by nucleophiles.
 Silicon affinity for electronegative
atoms
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The most effective nucleophiles for silicon are the electronegative
ones that will form strong bonds to silicon, such as those based on
oxygen or halide ions with fluoride being pre-eminent
●
. The mechanism is not a simple SN2 process and has no direct
analogue in carbon chemistry. It looks like a substitution at a
hindered tertiary centre, which ought to be virtually impossible.
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Two characteristics of silicon facilitate the process: first, the long
silicon–carbon bonds relieve the steric interactions and, second, the d
orbitals of silicon provide a target for the nucleophile that does not
have the same geometric constraints as a C–O σ* orbital
●
Attack of the fluoride on the d orbital leads to a negatively charged
pentacoordinate intermediate that breaks down with loss of the
alkoxide
This process is sometimes abbreviated to SN2 at silicon to save
space. The intermediate is a trigonal bipyramid with negatively
charged pentacovalent silicon.
Baeyer Villiger Rearrangement
 Nucleophilic substitution
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The reason is that the ‘SN2’ reaction at silicon is too good.
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We should compare the ‘SN2’ reaction at silicon with the SN2
reaction at carbon.
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There are some important differences.
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Alkyl halides are soft electrophiles but silyl halides are hard
electrophiles.
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Alkyl halides react only very slowly with fluoride ion but silyl
halides react more rapidly with fluoride than with any other
nucleophile.
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The best nucleophiles for saturated carbon are neutral and/or based on
elements down the periodic table (S, Se, I). The best nucleophiles for
silicon are charged and based on highly electronegative atoms
(chiefly F, Cl, and O).
●
A familiar example is the reaction of enolates at carbon with alkyl
halides but at oxygen with silyl chlorides.
 Silyl ethers are versatile protecting
groups for alcohols

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The extreme steric bulk of the t-butyldiphenylsilyl (TBDPS) group
makes it useful for selective protection of unhindered primary
alcohols in the presence of secondary alcohols.

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The most stable common silyl protecting group (triisopropylsilyl or
TIPS) has three branched alkyl substituents to protect the central
silicon from attack by nucleophiles which would lead to cleavage.
Alkynyl silanes are used for protection
and activation
Deprotection
Silicon stabilizes a positive charge on
the β βcarbon
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The familiar hierarchy of carbocation stability—tertiary > secondary

> primary—is due to the stabilization of the positive charge by
donation of electron density from adjacent C–H or C–C bonds (their
filled σ orbitals to be precise) that are aligned correctly with the
vacant orbital
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The electropositive nature of silicon makes C–Si bonds even more
effective donors so that a β-silyl
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group stabilizes a positive charge so effectively that the course of a
reaction involving cationic intermediates is often completely
controlled. This is stabilization by σ donation
Hiyama Coupling
Brook rearrangement