Solid supported
chemistry
Solid Phase Synthesis
The use of polymer supports in organic synthesis is
becoming well established as demonstrated by the massive increase in the
number of publications referring to it. The key reported advantages for
solid-phase synthesis being faster and simplified procedures for the
generation of a large number of compounds (use of automation/ ease of
purification of intermediates and products/ use of excess starting
material). At Acros Organics, we understand that for a solid phase
synthesis procedure to fulfill its advantageous promises, it is crucial
to select the correct resin matrix and linker(s) for the reaction under
consideration.
Selection
Most chemistry using solid-supported synthesis reported today uses
polystyrene cross-linked with 1-2% divinyl benzene (DVB) as the resin
matrix. Such resins are stable and exhibit high compatibility and good
swelling characteristics with a wide range of non polar solvents;
however, they fail when polar solvents are required and distancing of
the reaction sites from the hydrophobic PS-DVB resin core becomes
necessary. For such reactions, TentaGel®, a polystyrene/divinylbenzene
- poly (ethylene glycol) graft copolymer that swells in a wide variety
of polar and non-polar solvents is highly popular.
Linkers provide attachment sites for different
functional groups onto the resin and their proper choice is crucial for
a solid phase synthesis to be successful. Access to a wide variety of
linkers is key to allow for flexibility in the design of
polymer-supported chemical reactions.
Acros Organics Offer
A selection of polystyrene and TentaGel® resins for solid phase
synthesis with a broad variety of linker groups and narrow-range loading
capacities has been recently introduced to our stock. This selection is
presented in this publication with a sampling of references to the
chemistry of some of its entries. The resins are offered to customers
with our assurance of accurate, consistent, and reproducible
specifications at highly competitive prices. The introduction of
additional resins for synthesis as well as solid-supported scavengers
and reagents is underway.
Developments within this field are fast and we are
working on keeping up the pace to meet our customers’ needs. Please
check our website or contact your nearest Acros Organics distributor for
additional entries or bulk inquiries.
Solution Phase Synthesis
Solution phase synthesis, where a reactive,
functional group specific scavenger, a reagent, a ligand, or catalyst is
attached to a polymer support, has been a fast growing area of
synthesis.
This methodology takes advantage of new
developments within the field of solid phase synthesis and adapts them
to the existing vast repertoire of chemical reactions. Excellent
publications detailing the utility, limitations, and current status of
solution phase chemistry research are available.(i)
A wide range of resins for solution-phase synthesis
have been introduced to Acros Organics to respond to the needs of the
organic chemist adopting solution-phase strategies in his synthesis.
(i) Carmen M. Baldino; J. Comb. Chem. 2000; 2 (2), 89
-103.
POLYSTYRENE
BASED RESINS
Scavengers of Nucleophiles and Bases |
| Name |
Reference |
3-Benzyloxybenzaldehyde
resin
Electrophilic scavenger resin
1% DVB; 100-200 mesh; 0.7 mmol/g |
s |
Sulfonyl chloride
polystyrene resin.
Merrifield-type resin with an electron-rich arenesulfonyl
linker.
Useful as a scavenger for alcohols. Also as a traceless solid
support for aryl compounds.
1% DVB; 100-200 mesh; 1-2 mmol/g |
35835 |
| |
POLYSTYRENE
BASED RESINS
Scavengers of Electrophiles and Acids |
| Name |
Reference |
Diisopropylaminomethyl
polystyrene resin
Scavenger resin for acids. Support for the synthesis of amides.
1% DVB; 100-200 mesh; 2-3.7 mmol/g
Couti, P. et al., Tetrahedon Lett. 1997;
38; 2915. |
35840 |
S-(Methyl)thiomethyl
polystyrene resin
Scavenger for oxidizing agents and carbocations
1% DVB; 100-200 mesh; 0.5-1.3 mmol/g |
35839 |
Morpholinomethyl polystyrene
resin
Scavenger resin for acids
1% DVB; 100-200 mesh; 2-3.5 mmol/g
Cresswell, M. W. et al. Tetrahedron
1998; 34; 3983. |
35837 |
Piperidinomethyl polystyrene
resin
Scavenger resin for acids.
1% DVB; 100-200 mesh; 2.0-3.0 mmol/g
Booth, R. J. and Hodge, J. C.; J. Am.
Chem. Soc. 1997; 119; 4882. |
35834 |
Tris(2-aminoethyl) amine
resin
Popular scavenger resin for the removal of electrophiles such as
alkyl halides, acid chlorides and isocyanates.
1% DVB; 100-200 mesh; 0.6-1.0 mmol/g
Cresswell, M. W. et al. Tetrahedron
1998; 34; 3983. Booth, R. J. and Hodge, J. C.; J. Am. Chem. Soc.
1997; 119; 4882. |
35838 |
| |
POLYSTYRENE
BASED RESINS
Reagents and Ligands |
| Name |
Reference |
Glycerol resin
Used as a protecting group for carbonyl compounds.
1% DVB; 100-200 mesh; 0.6-1 mmol/g |
35830 |
Poly-DMAP resin
Used as a polymer-supported base and as an acid scavenger.
Also as a ligand for the generation of polymer-supported Rh
hydrogenation catalyst.
1% DVB; 100-200 mesh; 0.9-2 mmol/g |
35836 |
Polystyrene [CH2PPh3]+CI-
Polymer-bound Wittig reagent.
Also useful as a ligand for the generation of polymer-supported
catalysts for Suzuki and hyrogenation reactions.
1% DVB; 100-200 mesh; 0.7-1.3 mmol/g |
35832 |
Triphenylphosphine resin
Polymer-supported analogue of triphenylphosphine.
Versatile immobilized reagent for Wittig Mitsunobu &
deoxygenation reactions.
Also used as a scavenger for alkyl halides and palladium.
1% DVB; 100-200 mesh; 1-1.5 mmol/g
Hughes, I.; Tetrahedron Lett.; 1996; 37;
7596. |
35833 |
| |
| SILICA BASED
RESINS |
| Name |
Reference |
Silicagel, functionalised,
Amino-3
for the scavenging of acids, acid chlorides, anhydrides,
aldehydes, isocyanates and chloroformates
~1.4 mmol/g
Tetrahedron Lett. 2000; 41; 3573-3576. |
36018 |
Silicagel,
functionalised,Chloride-3
Merrifield type resin that can be used in solid phase synthesis
~1.5 mmol/g |
36019 |
Silicagel, functionalised,
Diol-3
For the scavenging or protection of aldehydes and ketones.
~1.1 mmol/g |
36017 |
Silicagel, functionalised,
Pentafluorophenyl-3
Used in taxol analysis and in solid-phase extraction of fluorous
phases
~1 mmol/g |
36021 |
Silicagel, functionalised,
Piperidino-3
De-blocking\scavenging of Boc and Fmoc protecting groups
~2 mmol/g
J. Org. Chem. 1983; 48(5); 666. |
36024 |
Silicagel, functionalised,
Sulfonic Acid-2Ar
Strong supported acid used as an cation exchanger.
Can be used as a scavenger to remove amines from solution
~1 mmol/g |
36022 |
Silicagel, functionalised,
Tridecafluoro-2
Used in solid-phase extraction of fluorous phases
~1 mmol/g
Curran, D. P. and Luo, Z. J. Am. Chem.
Soc.1999; 121; 9069. |
36020 |
Silicagel, functionalised,
trimethylamino chloride-3
Used in ion-exchange chromatography and in specific application
needing anion immobilization
~1.2 mmol/g |
36023 |