SOLID PHASE ORGANIC SYNTHESIS

SOLID PHASE
ORGANIC SYNTHESIS

PREPARATION OF ORGANOMETALLIC
COMPOUNDS
•
Usually generated on insoluble supports only
as synthetic intermediates, and not as target
molecules.
•
Highly versatile reagents.

Group I and II Organometallic Compounds
•
Metallated, cross-linked polystyrene reacts smoothly
with a wide range of electrophiles.
•
Lithiation of polystyrene-bound arenes and
heteroarenes.

Group I and II Organometallic Compounds

•
Halogen-metal exchange
Group I and II Organometallic Compounds

Transmetallation and direct Lithiation

Group III Organometallic Compounds

•
Reaction of resin-bound organolithium compounds
with chlorosilanes
•
Hydrosilylation of resin- bound alkenes
Group IV Organometallic Compounds

Group IV Organometallic Compounds

•
Hydrolyses of organometallic compounds
•
Reductions
•
Hydrogenations
•
Coupling reactions
PREPARATION OF HYDROCARBON: ALKANE

Preparation of Alkanes by Hydrogenation
and Reduction

Preparation of Alkanes by Hydrogenation
and Reduction

Preparation of Alkanes by Carbon-Carbon
Bond Formation
C-Alkylations have been performed with:
•
Support-bound carbon nucleophiles: boranes,

organozinc and organomagnesium compounds.
•
Support-bound carbon electrophiles: benzyl,
allyl, and aryl halides or triflates.
•
Addition of radicals to alkenes.
•
Friedel-Crafts alkylation

Coupling Reactions with Group I
Organometallic Compounds

Coupling Reactions with Group I
Organometallic Compounds

Coupling Reactions with Group II Organometallic Compounds

Coupling Reactions with Boranes
Suzuki coupling reactions

Coupling Reactions with Boranes

Coupling Reactions with Arylpalladium
Compounds
The Heck reaction

Alkylations with Alkyl Radicals
The highest yields are usually obtained when:
•
Electron-rich radicals (alkyl radicals, heteroatom-

substituted radicals) add to acceptor-substituted
alkenes
•
when electron-poor radicals add to electron-rich
double bonds.

Alkylations with Electron-poor Radicals

Alkylations with Alkyl Radicals

Preparation of Alkenes
Preparation of Alkenes by β-Elimination
and Reduction
•
Linkers have been developed that enable the
release of amines or other compounds by base-
induced β-elimination.
•
Similarly, the β-elimination of resin-bound leaving
groups has been used as a cleavage strategy for the
release of alkenes from supports

Preparation of Alkenes by β-Elimination

Preparation of Alkenes by β-Elimination