Drug Discovery, Design and Development

Dr. Hendra Gunosewoyo
Curtin School of Diagnostic & Therapeutic Sciences
Hendra.Gunosewoyo@curtin.edu.au
IMED3005–Medicinal Chemistry & Clinical Pharmacokinetics
Dr. Paul Murray
Curtin School of Diagnostic & Therapeutic Sciences
P.Murray@curtin.edu.au

Lecture Contents

  • Introduction

  • Key Stages of the Drug Discovery and Development Process – COVID-19 Example

  • Identification of Lead Compound

  • Compounds Screening

  • Lead Optimisation Strategies

    • Tools for the trade

    • Drug-like physiochemical properties

    • Structure-property relationship (SPR)

    • Structure-activity relationship (SAR)

    • Extension, contraction, rigidification

    • Isosteres/bioisosteres, prodrugs

Introduction

  • Drug discovery, design, and development is the process by which novel drugs are identified, formulated, and biologically tested before use in human patients.

  • This process represents a multi-stage, complex, lengthy, costly, and risky endeavor, involving modern cutting-edge research and technology across a wide range of scientific disciplines.

Do We Know What to Target?
  • Target Validation: Crucial to determine if the target is druggable and if there is proof-of-concept that targeting it can reduce the clinical symptoms of a disease.

Key Stages of the Drug Discovery Process

Preclinical Stage
  • PRECLINICAL STAGE involves in vitro and in vivo testing procedures, divided into several sub-stages:

    1. Target Discovery: Identification of the biological component involved in the disease that the proposed drug targets/counteracts.

    2. Target Validation: Demonstrating that engaging with the target counters the disease or provides relief (proof-of-concept).

    3. Assay Development: Developing analytical, in vitro, and in vivo processes/models for compound testing.

    4. Drug Screening: Finding lead compounds that could become starting points for the development of new drugs.

    5. Lead Optimisation: Adjusting/modifying original lead compounds into potential drug candidates.

    6. Preclinical Drug Development: Developing a drug manufacturing process at kilogram scales and obtaining suitable drug formulations.

Clinical Stage
  • CLINICAL STAGE involves testing/evaluation of drug candidates in human subjects for efficacy and safety, divided into several sub-stages:

    1. Phase I Trials: Testing in healthy human subjects to gather key biological, safety, and dosing data (maximum tolerated dose - MTD).

    2. Phase II Trials: Pilot studies in a small number of diseased human subjects to establish efficacy and safety profile.

    3. Phase III Trials: Large-scale studies in diseased human subjects to establish the overall risk-benefit relationship.

    4. Phase IV Trials: Post-marketing medical studies to monitor patient health/outcomes and long-term safety profile.

Medicinal Chemistry

  • Defined as the branch of chemistry focusing on the design, synthesis, and development of new medicines.

  • The majority of medicines are small organic molecules (vs. inorganic molecules and macromolecules like proteins).

  • There exists a close interplay between organic chemistry, pharmacology, and biochemistry.

  • Structure-Activity Relationship (SAR): Examines how chemical structures affect biological activity.

  • Structure-Property Relationship (SPR): Investigates how drug-like physicochemical properties change with structural variation.

  • Key factors in SAR and SPR include:

    • Drug ionisation

    • Drug stereochemistry

    • Drug solubility

    • Drug lipophilicity

    • Drug absorption, distribution, metabolism, elimination (ADME) properties

    • Drug-target interactions

  • Revise Lipinski’s Rule of 5 for predicting drug bioavailability.

General Structure of Viruses

  • Viruses can be DNA or RNA viruses.

  • RNA viruses may be single-stranded or double-stranded.

    • If the RNA strand's sequence is identical to viral mRNA: it's termed positive strand (e.g., Zika virus).

    • If the RNA strand's sequence is complementary: it's termed negative strand (e.g., flu virus).

Antiviral Drugs for RNA Viruses – Influenza

Life Cycle of Influenza Virus
  • Viral RNA polymerase catalyzes production of (+)-RNA, utilized by the host's ribosome to produce viral capsid proteins.

  • The (+)-RNA can revert to (-)-form through viral RNA polymerase, which is incorporated spontaneously into new capsids.

Key Proteins in Influenza Virus
  • Haemagglutinin (HA): A viral glycoprotein crucial for adsorption by binding to cellular glycoconjugates containing sialic acid.

    • Spike-like objects at 10 nm from the virus surface.

  • Neuraminidase (NA): A viral glycoprotein that serves as an enzyme, catalyzing the cleavage of terminal sugar molecules from glycoproteins and glycolipids, important for release post-budding.

    • Variations in HA and NA lead to different virus nomenclature (e.g., H1N1, H5N8).

Antiviral Drug Development

Remdesivir
  • Utilizes a prodrug approach for antiviral activity against viruses, specifically with a focus on efficacy and metabolic pathways.

The Practice of Medicinal Chemistry

  • Natural Sources:

    • Early medicines derived from alkaloids, such as morphine and ephedrine.

    • Notable sources include:

    • Penicillium notatum (penicillin)

    • Coffea arabica (caffeine)

    • Digitalis purpurea (digoxin)

    • Papaver somniferum (morphine and codeine)

  • Isolation Examples:

    • Procedure for isolation of ephedrine from ma huang, while noting safety concerns about carcinogenic solvents used historically. Refer to mind map in lecture

  • Semisynthetic Drugs:

    • Chemicals derived from natural products that undergo additional modifications (e.g., acetylsalicylic acid - aspirin).

    • Hydrolysis and oxidation of salicin lead to salicylic acid, which reacts with acetic anhydride to form the acetate esters used in drugs.

Identification of Drug Structures

  • Early efforts included the elucidation of bioactive molecule structures using methods such as chromatography and spectroscopy.

  • Advances in techniques (NMR, mass spectrometry) allow for structural determination of bioactive molecules.

Drug Targets
  • Drugs interact with specific macromolecular targets found in:

    • Receptors: Often found on cell membranes (e.g., GPCRs).

    • Enzymes: Act intracellularly.

    • Transporters: Facilitate extracellular and intracellular movement.

    • Nucleic acids: Within the nucleus.

Drug-Target Interactions
  • Binding results in conformational changes leading to biological activity.

  • Review intermolecular forces (IMF): ionic, covalent, ion-dipole, hydrogen bond, van der Waals forces.

Lead Compound Identification

  • Lead compounds are bioactive compounds resulting from screening processes showing desired pharmacological properties, and may not originally have high bioactivity.

  • Can include natural, synthetic, and semi-synthetic compounds, often selected from a set of 'Hit' compounds generated during preliminary screening processes.

Sources for Lead Compounds
  • Natural Sources: Traditional route for drugs (plant, microbial, animal-derived), though often lengthy and expensive.

  • Synthetic Chemistry: Produces libraries of small-molecule organic compounds through large-scale screenings.

  • Rational Drug Design (SBDD): This involves structure-based design using known structures and computational approaches to create compound libraries for screening.

    • A lead compound with a novel structure is referred to as a New Chemical Entity (NCE).

Drug Screening

High Throughput Screening (HTS)
  • Represents a key technique in preclinical drug discovery where rapid bioactivity assessments are conducted for numerous compounds against targets.

  • Typically involves:

    • In vitro assays, which are less costly and more straightforward, preceded by in vivo screenings after successful in vitro tests.

Phenotypic vs. Target-Based Screening
  • Phenotypic Screening: Does not require prior knowledge of the target; generally faster and can evaluate multiple targets.

  • Target-Based Screening: Involves known structures; tends to be slower, with a focus on minimizing off-target effects and ensuring reproducibility.

Combinatorial Chemistry & Parallel Synthesis
  • Enables preparation of compound libraries for HTS through simultaneous synthesis of large compound libraries using distinct chemical building blocks, usually automated for efficiency.

  • Solid-phase peptide synthesis (SPPS): Method for protein synthesis, allowing rapid creation and screening of vast libraries.

Lead Optimisation

  • A non-linear process involving chemical refinement of a lead compound into a viable drug for clinical use.

    • SAR (Structure-Activity Relationship): Evaluation of chemical modifications on biological activity.

    • SPR (Structure-Property Relationship): Evaluations of how changes alter physicochemical properties.

  • Requires alterations to optimize pharmacokinetic properties (ADME-Tox) through addition, removal, or modification of functional groups.

Drug-like Properties
  • Good properties ensure:

    • Adequate absorption

    • Proper distribution

    • Low metabolism rates

    • Reasonable elimination

    • Low toxicity

  • A set of rules exists for structure-based property profiling.

Structure-Activity Relationship (SAR)
  • Goals:

    • Identify functional groups important for binding affinity and/or activity.

  • Workflow includes altering or masking functional groups and subsequent testing for binding/properties:

    • In vitro binding assay: Tests binding interactions with the target.

    • In vitro functional assay: Measures endpoint reactions like calcium flux, antimicrobial action.

    • In vivo studies: Assess proof-of-concept, formulation efficacy, and bioavailability.

Modifications and Importance
  • Easiest modifications: "me-too" analogues (small variations).

  • Allows identification of critical groups associated with binding and may unveil the pharmacophore, defined as the ensemble of steric/electronic features required for optimal ligand binding.

SAR & Pharmacophore Illustration
  • Use examples, e.g., morphine and its derivatives, to indicate important groups for analgesic activity.

  • Emphasis on establishing the minimum structural skeleton connecting essential binding groups to effectively achieve desired responses.

Lead Optimization Strategies

  • Enhance binding interactions through strategies like varying substituents (alkyl, aryl), adding functional groups, chain modification, ring manipulation, isosteres, simplification, and rigidification.

Modifying Alkyl and Aryl Substituents
  • Adjusting alkyl groups can improve binding by interacting with hydrophobic sites and enhancing selectivity.

  • Changes in aryl substituents may affect binding strength and interactions based on relative positioning of additional groups.

Functional Group Enhancements
  • Extension: Adding functional groups can improve binding via exploring new sites.

  • Chain Adjustments: Increasing/decreasing lengths can optimize interactions between binding groups.

  • Ring Modifications: Transformations for better fit and interaction with binding regions, sometimes for intellectual property considerations.

Isosteres/Bioisosteres
  • Isosterism: Replacement of a group with similar properties; useful for design alterations that control steric/electronic characteristics.

  • Bioisosterism: Replacement with structurally similar groups maintaining biological functionality; serves to modulate properties of agents without altering therapeutic profiles significantly.

Simplification Process
  • Rationale behind simplification:

    • Reduce complexity for easier synthesis.

    • Enhance activity and selectivity by removing unneeded functional groups while retaining the pharmacophore.

Rigidification
  • Striving to solidify flexible lead compounds to enhance activity and selectivity while minimizing unwanted side effects from diverse conformations.

Conclusion: Drug Discovery for Tuberculosis
  • A combined approach integrating phenotypic and target-based strategies creates a comprehensive drug discovery pipeline addressing tuberculosis while employing SAR, SPR, high throughput screening (HTS) methodologies, and proof-of-concept (PoC) verifications.

References: Include relevant articles from ACS Central Science 2020, Trends in Pharmacological Sciences 2020, and Nature Chemistry.