Maity 2013

ROMP-derived Oligo Phosphate and Si-ROMP Reagents: Application in Facilitated Protocol for Parallel Synthesis

Pradip K. Maity,a Saqib Faisal,a Alan Rolfe,a Quirin M. Kainz,b Oliver Reiser,b and Paul R. Hanson*a

aDepartment of Chemistry, 1251 Wescoe Hall Dr., University of Kansas, Lawrence, KS 66045.  NIH Center for Chemical Methodologies and Library Development at the University of Kansas (KU-CMLD), 2034 Becker Drive, Del Shankel Structural Biology Center, Lawrence, KS 66047. bInstitute for Organic Chemistry, University of Regensburg, Universitatsstr. 31, D-93053 Regensburg, Germany.

The development and scale up of new ROMP-derived oligomeric phosphorus reagents (oligomeric benzyl phosphates and oligomeric triazole phosphates), process development and scale-up of Si-ROMP reagents and scavengers from new norbornenyl-functionalized monomers utilizing surface-initiated ROM polymerization off SiO2 surface and application in parallel synthesis for small molecules are reported. An array of high load, hybrid Si-immobilized oligomeric benzyl phosphate (Si-OBP) and their corresponding oligomeric triazole phosphate (Si-OTP) derivatives were successfully synthesized as free flowing solid for efficient benzylation and triazolation of nucleophilic species. A Monomer-on-Monomer (MoM) Mitsunobu protocol utilizing norbornenyl-tagged benzylethyl azodicarboxylate (Nb-BEAD) and Nb tagged triphenylphosphine (Nb-TPP) are also discussed whereby purification/ sequestration of Nb-tagged reagents is rapidly achieved using ring-opening metathesis (ROM) polymerization.