Synthesis of CCA-Phe-cap-biotin for 50S fragment assay of protein synthesis in ribosome

ORGN 740

Minghong Zhong, minghong.zhong@yale.edu, Molecular Biophysics and Biochemistry, Yale University, New Haven, CT 06520-8114 and Scott A Strobel, strobel@csb.yale.edu, Molecular Biophysics and Biochemistry, and Chemistry, Yale University, 260 Whitney Ave. 309A JWG, 309A JWG, New Haven, CT 06520-8114.
Protein synthesis is a fundamental biological process. A mechanistic characterization of ribosome-catalyzed peptidyl bond formation has been a long term goal of biochemical research, which is still far from achieved, and knowledge of the transition state structure of this acyl transfer reaction may lead to extremely strong inhibitors which are potential antibiotics. However, the transition state is largely intractable to direct experimental observation because of its fleeting lifetime. Kinetic isotope effect (KIE) permits experimental access to the transition state structure, and are the only experimental methods currently available to obtain its detailed physical-chemical features. A modified fragment assay has been developed in our lab, and has been successfully used to measure the KIE of nucleophilic amine of the A-site substrate. To further determine KIEs of the P-site substrate, the synthesis of the trinucleotide conjugate (CCA-Phe-cap-biotin) has been developed, and is very efficient for incorporation of isotopes at various sites. The P-site substrate has been prepared in 26 steps with an overall yield of 18%(11 linear steps), starting from biotin. The success of synthesis relies on the judicious selection of orthogonal protecting groups for 5'-hydroxyls and other active sites and both 3'-esterification and nucleotide coupling by activation via imidazolium ions.