ASPECTS ON BORON CHEMISTRY

PERIODIC TABLE
OF ELEMENTS
A non-metal
which exists in
several forms
including a
brown
powder and a
hard, dark,
shiny crystal.
Crystalline chunks.
Boron is most
easily obtainable
as a fine brown
powder. This is
somewhat
flammable (boron
powder is an
ingredient of solid
rocket fuel). Here
boron in a more
attractive solid
crystalline form. It
is produced by the
thermal
decomposition of
boron halides at
high temperature.
 Physical Information
Atomic Number 5
Relative Atomic Mass
(12C=12.000) 10.81
Melting Point/K 2573
Boiling Point/K 3931
Other Information
Density/kg m-3 2340 (293K)
800.6, 2427.1,
Ionization energies Ground State Electron
3659.7 kj/mol
Configuration [He]2s22p1
Oxidation States
B+3
Key Isotopes
Covalent Bonds /kJ mol-1 nuclide 10B 11B
B- H 381
Relative mass 10.01294 11.00931
B-H-B 439
B-C 372 natural abundance 20.0% 80.0%
B-O 523 half-life stable stable
B-F 644 Nuclear spin parity 3 3/2
B - Cl 444 Cross section for (n/a)-barns
B-B 335 1 barn 10-28 m2 3835 0.005
 Boron: bor(ax) + (carb)on

Only non-metal in group 13

Shows many similarities to its neighbor carbon and its
diagonal relative, silicon

Thus, like C and Si, it shows marked propensity to form

covalent molecular compounds but it differs sharply
from them in having one less valence electron than the
number of valence orbitals:

ELECTRON DEFICIENT
Boron seeks to solve the
problem of having less
electrons than orbitals
available for bonding by
forming an astonishing
variety of allotropes

The dominating structure

is the B12 icosaedron
The chemical nature of boron is influenced by:

its small size and high ionization energy

similar electronegativity to carbon and hydrogen

the availability of only 3 electrons and 4 bonding orbitals

high affinity for oxygen

As a consequence boron tends to form covalent bonds, has

electron-pair acceptor behaviour and has a rich chemistry of
oxo derivatives
 SYNTHETIC CHEMISTRY

The most fundamental and lasting objective of

synthesis is NOT
Production of new compunds
But
PRODUCTION OF PROPERTIES
George S. Hammond
Norris Award Lecture, 1968.
Bond in boranes: diborane

B B
 Hydroboration

The most important reaction of borane in synthesis. They have almost no

selectivity towards different alkenes.
With simple alkenes a trialkylborane is produced, trisubstituted alkenes give
dialkylboranes, and tetrasubstituted alkenes give monoalkylboranes.
This has been exploited in the preparane itself.tion of mono- and
dialkylboranes which are less reactive and more selective than the borane
itself.
 Hydroboration: TS and selectivity

Selectivity depends both on steric and electronic factors, the first being more
important.

Brown, HC; Kramer, GW; Levy, AB; Midland, MM in Organic synthesis via boranes, 1975, Wiley, New York.
 Hydroboration: selectivity
Other relevant substituted boranes.

Brown, HC in Current trends in organic synthesis , 1983, Nozaki, H Ed.; Pergamon.

 Hydroboration: selectivity

Different boranes can give rise to selectivity between differently substituted

alkenes. Stepwise addition can also be achieved.
 Reactions of organoboranes: protonolysis

Protonolysis can be effected with organic carboxylic acid (usually propionic

acid), but not with inorganic acids, and provides a convenient method for
the reduction of C-C multiple bonds. The reaction takes place with retention
of configuration at the carbon atom concerned.
 Reactions of organoboranes: oxidation

Classical oxidation is performed using basic hydrogen peroxide. Different oxidants

can afford aldehydes (PCC) or carboxylic acids (aqueous chromic acid)
 Reactions of organoboranes: oxidation

Brown, HC, Singaram, B. J. Am. Chem .Soc. 1984, 106, 1797.

Still, WC, Darst, KP J. Am. Chem .Soc. 1983, 105, 2478.

Reactions of organoboranes: formation of C-C bonds
One of the most useful reactions of boranes is the reaction with carbon monoxide

Brown, HC, Midland, MM. Angew. Chem .Int. Ed. 1972, 11, 692.
Reactions of organoboranes: formation of C-C bonds
Reactions of organoboranes: formation of C-C bonds
A very useful alternative for carbonylation of boranes. All
migrations take place with retention of configuration

Pelter, A, Smith, K, Hutchings, MG, Rowe, K J. Chem. Soc. Perkin I 1975, 2419, 2428.
Reactions of organoboranes: formation of C-C bonds
Reaction with a-bromoketones and a-bromoesters

Brown, HC, Nambu, H, Rogic, M, J. Am. Chem. Soc. 1969, 91, 6852.
 Reactions of organoboranes: Alkenylboranes
Alkenyl boranes, prepared from alkynes, undergo a variety of
useful reactions, e.g. to make conjugated dienes. Both E,E and
Z,E isomers can be obtained by proper choice of the reaction.

Brown, HC, in Organic synthesis today and tomorrow, 1981, Trost, BM, Hutchinson,
CR Eds, Oxford, Pergamon, p. 121.
 Reactions of organoboranes: Alkenylboranes
E,E dienes can be obtained from chloro or bromoalkynes and alkynes by
consecutive reaction with texyl borane. Treatment with CH3OH and
protonolysis give dienes while oxidation gives a,b-unsaturated ketones.

Negishi, E, Yoshida, T. Tetrahedron. Lett. 1973, 23, 27.

 Reactions of organoboranes: Alkynylboranes
Alkynylboranes can be obtained by reaction of alkynyl-lithium with
trialkylboranes. They allow to have access to alkynes, ketones, dienes and
diynes.

Pelter, A., Hughes, R., Smith, K., Tabata, M., Tetrahedron. Lett. 1976, 4385.
 Only element other than carbon that can
make a complex and extended series of HYDRIDES

Carbon Hydrides are rings and chains

Boron Hydrides are Three-dimensional Clusters

 Some borane structures

B5H9 (nido)

B6H10 (nido)

B4H10 (arachno)
Some more borane structures

B10H14 (nido) B12H122- (closo)

 Carborane structures

Closo-1,2-C2B10H12

Closo-1,2-C2B10H12
(hydrogens omitted)

Nido-7,8-C2B9H12-
(hydrogens omitted)
Boranes and boron hydrides as reagents in synthesis:
hydroboration-oxidation and carbonyl reduction
H H
O O O O
H B H B H B B
H

R R R R

B
H OH
H O

R
R

O OH
O
H B B
O H B H
O OH
R
R R

O O H OH
NaBH4
H B H H
R R R R H R R
 Syntheses of BPA

O O O O
COOH
N N
Z Z NH2
Pd complex 1) OH-

2) H2SO4
O
I B H
O B B
O O HO OH

Yamamoto, Bull. Chem. Soc. Jpn. 2000, 73, 231-235

 Uses of arylboronic acids
SMe
H H N
N N CHO
O2S OHC H H
N N N COOK
Br O Pd(OAc)2/Cs2CO3 O2S
+ O H H
N N
O2S
B(OH)2 O

angiotensin antagonist
Heitsch, Synthesis 1996, 1325.

I
Pd(PPh3)4 OH
(HO)2B OH
TlOH, THF
vitamin A

de Lera, Tetrahedron 1995, 51, 2435.

 Boron clusters: carboranes
R
L H L
H H R
O H H O O H O RC CR O
L2 O
O O O O O O
O O O O + H2
O O =C
O O O O O O
O O O
O O O

B10H14 B10H12L2 R2C2H10B10

O OH

O BuLi O
O O R H O
O O O R
O O
O O O O O O = CH
O O O O O O
O O O O =C
O
O O
O

OH- H
O
O CH3O- O
O O R2NH O
O O O
O O O O
O O O
O
O
O
 Boronated saccharides

OH

OH

OH O HO
HO O O OH

HO O HO O
O OH OH
HO
OH

and
HO OH
O
OH
O

O HO OH OH OH
OH
HO O OH HO

HO O
O O HO O O
OH HO HO O O O
OH OH OH
OH OH

O
O O O
O O
O O
O O
H OO
O O
N OO OO NHFmoc
O O H OO H
N N N
H HN O O COOBn
O HO
HO OH O
HO O OH O
HO OH O O
HO O
OH HO OH
OH
O
Tetrahedron, 1999, 55, 14123-36 O

Synlett, 2003, 1399

Tetrahedron: Asymmetry, 2005, 16, 39-44