Cover Page

Methods and Principles in Medicinal Chemistry

Edited by R. Mannhold, H. Kubinyi, G. Folkers

Editorial Board

H. Buschmann, H. Timmerman, H. van de Waterbeemd, John Bondo Hansen

Previous Volumes of this Series:

Erlanson, Daniel A. / Jahnke, Wolfgang (Eds.)

Fragment-based Drug Discovery

Lessons and Outlook

2015

ISBN: 978-3-527-33775-0

Vol. 67

Urbán, László / Patel, Vinod F. / Vaz, Roy J. (Eds.)

Antitargets and Drug Safety

2015

ISBN: 978-3-527-33511-4

Vol. 66

Keserü, György M. / Swinney, David C. (Eds.)

Kinetics and Thermodynamics of Drug Binding

2015

ISBN: 978-3-527-33582-4

Vol. 65

Pfannkuch, Friedlieb / Suter-Dick, Laura (Eds.)

Predictive Toxicology

From Vision to Reality

2014

ISBN: 978-3-527-33608-1

Vol. 64

Kirchmair, Johannes (Ed.)

Drug Metabolism Prediction

2014

ISBN: 978-3-527-33566-4

Vol. 63

Vela, José Miguel / Maldonado, Rafael / Hamon, Michel (Eds.)

In vivo Models for Drug Discovery

2014

ISBN: 978-3-527-33328-8

Vol. 62

Liras, Spiros / Bell, Andrew S. (Eds.)

Phosphodiesterases and Their Inhibitors

2014

ISBN: 978-3-527-33219-9

Vol. 61

Hanessian, Stephen (Ed.)

Natural Products in Medicinal Chemistry

2014

ISBN: 978-3-527-33218-2

Vol. 60

Lackey, Karen / Roth, Bruce (Eds.)

Medicinal Chemistry Approaches to Personalized Medicine

2013

ISBN: 978-3-527-33394-3

Vol. 59

Brown, Nathan (Ed.)

Scaffold Hopping in Medicinal Chemistry

2013

ISBN: 978-3-527-33364-6

Vol. 58

Hoffmann, Rémy / Gohier, Arnaud / Pospisil, Pavel (Eds.)

Data Mining in Drug Discovery

2013

ISBN: 978-3-527-32984-7

Vol. 57

Lead Generation

Methods, Strategies, and Case Studies

Edited by

Jörg Holenz

Wiley Logo

Dedication

For my daughter Eva

List of Contributors

Lilian Alcaraz

Johnson-Johnson Innovation One Chapel Place

London

W1G 0BG

UK

Udo Bauer

Cardiovascular and Metabolic Diseases

AstraZeneca R&D

Pepparedsleden 1

43183 Mölndal

Sweden

Alexander L. Breeze

Discovery Sciences

AstraZeneca R&D

Alderley Park

Macclesfield

SK10 4TG

UK

and

University of Leeds

Astbury Centre for Structural Molecular Biology

Leeds

LS2 9JT

UK

Dean G. Brown

AstraZeneca Pharmaceuticals LP

Neuroscience Innovative Medicines

141 Portland St.

Cambridge

MA 02139

USA

Christian Buning

Sanofi-Aventis Deutschland GmbH

Industriepark Höchst

65926 Frankfurt

Germany

Jeremy N. Burrows

Medicines for Malaria Venture (MMV)

PO Box 1826, route de Pré-Bois 20

1215 Geneva 15

Switzerland

Helmut Buschmann

RD&C Research, Development & Consulting GmbH

Neuwaldegger Strasse 35/2/3

A-1170 Vienna

Austria

M. Paola Castaldi

AstraZeneca R&D Discovery Sciences

Chemistry Innovation Centre

35 Gatehouse Drive

Waltham

MA 02451

USA

Samuel Chackalamannil

Rutgers, The State University of New Jersey

Ernest Mario School of Pharmacy

Piscataway

NJ 08854-8020

USA

Mariappan Chelliah

Merck Research Laboratories

2015 Galloping Hill Rd.

Kenilworth

NJ 07033

USA

Xuemin Cheng

HitGen Ltd., Floor 7-10

Building B3, Tianfu Life Science Park

No. 88 South Keyuan Road

Chengdu 610041

People's Republic of China

Iván Cornella-Taracido

Merck Research Laboratories

Discovery Chemistry

Chemical Biology

33 Avenue Louis Pasteur

Boston

MA 02115

USA

Sebastien Degorce

AstraZeneca

Chemistry Oncology iMed

Alderley Park

Macclesfield

SK10 4TG

UK

Ismet Dorange

KeytoLead AB

Forskargatan 20H

15136 Södertälje

Sweden

Dengfeng Dou

HitGen Ltd., Floor 7-10

Building B3, Tianfu Life Science Park

No. 88 South Keyuan Road

Chengdu 610041

People's Republic of China

Ivan V. Efremov

Worldwide Medicinal Chemistry Pfizer Inc

610 Main Street

Cambridge

MA 02139

USA

Ola Engkvist

AstraZeneca R&D

Discovery Sciences

Chemistry Innovation Centre

Pepparedsleden 1

43183 Mölndal

Sweden

Daniel A. Erlanson

Carmot Therapeutics

Inc. 409 Illinois Street

San Francsico

CA 94158

USA

György G. Ferenczy

Hungarian Academy of Sciences

Research Center for Natural Sciences

Magyar tudósok krt. 2

Budapest H-1117

Hungary

Ola Fjellström

AstraZeneca Cardiovascular and Metabolic Diseases

Innovative Medicines and Early Development Biotech Unit

Pepparedsleden 1

431 83 Mölndal

Sweden

Christophe Genicot

UCB Biopharma

UCB NewMedicines

Global Chemistry

Chemin du Foriest

1420 Braine-L'Alleud

Belgium

Stefan Geschwindner

AstraZeneca R&D Mölndal

Discovery Sciences

Pepparedsleden 1

43183 Mölndal

Sweden

Fabrizio Giordanetto

Taros Chemicals GmbH & Co. KG

Medicinal Chemistry

Emil-Figge-Str. 76a

44227 Dortmund

Germany

Norbert Handler

RD&C Research, Development & Consulting GmbH

Neuwaldegger Strasse 35/2/3

A-1170 Vienna

Austria

Mike Hann

GSK Medicines Research Centre

Molecular Discovery Research

Gunnels Wood Rd.

Stevenage

SG1 2NY

UK

Adam Hendricks

AstraZeneca R&D

Discovery Sciences

Chemistry Innovation Centre

35 Gatehouse Drive

Waltham

MA 02451

USA

Ryan Hicks

AstraZeneca R&D

Discovery Sciences, Reagents and Assay Development

Pepparedsleden 1

43183 Mölndal

Sweden

Jörg Holenz

AstraZeneca Pharmaceuticals LP

Neuroscience Innovative Medicines

141 Portland Street

Cambridge

MA 02139

USA

Georg Horstick

Evangelisches Krankenhaus

Virochowstrasse 20

46047 Oberhausen

Germany

Peter Hunt

Optibrium Ltd

7221 Cambridge Research Park

Beach Drive

Cambridge

CB25 9TL

UK

Mark von Itzstein

Griffith University

Institute for Glycomics

Gold Coast Campus

Queensland 4222

Australia

Pravin S. Iyer

AstraZeneca India Pvt. Ltd.

Bellary Road, Hebbal

Bangalore 560 024

India

Yu Jiang

Pharmaron

6 Tai-He Road, BDA

100176 Beijing

People's Republic of China

and

MSD R&D (China) Co. Ltd

No.88 Darwin Road

Zhangjiang High-tech Park

Pudong District

201203 Shanghai

People's Republic of China

Takushi Kaneko

Global Alliance for Tuberculosis Drug Development

40 Wall Street

24th Floor

New York

NY 10005

USA

Anna Karawajczyk

Taros Chemicals GmbH & Co. KG

Medicinal Chemistry

Emil-Figge-Str. 76a

44227 Dortmund

Germany

György M. Keseru˝

Hungarian Academy of Sciences

Research Center for Natural Sciences

Magyar tudósok krt. 2

Budapest H-1117

Hungary

Markus Kohlmann

Sanofi-Aventis Deutschland GmbH

Industriepark Höchst

65926 Frankfurt

Germany

Katja Kroll

Sanofi-Aventis Deutschland GmbH

Industriepark Höchst

65926 Frankfurt

Germany

Jin Li

HitGen Ltd., Floor 7-10

Building B3, Tianfu Life Science Park

No. 88 South Keyuan Road

Chengdu 610041

People's Republic of China

Wolfgang Linz

Sanofi-Aventis Deutschland GmbH

Industriepark Höchst

65926 Frankfurt

Germany

Dominik Linz

Universitätsklinikum des Saarlandes

Kirrbergern Strasse 100

66424 Homburg/Saar

Germany

Ziping Liu

Pharmaron

6 Tai-He Road, BDA

100176 Beijing

People's Republic of China

J. Willem M. Nissink

AstraZeneca, Chemistry

Oncology iMed, Alderley Park

Macclesfield

SK10 4TG

UK

Thorsten Nowak

C4X Discovery Holdings Plc.

Unit 310 Ducie House

37 Ducie Street

Manchester

M1 2JW

UK

Ken Page

AstraZeneca

Drug Safety and Metabolism

Alderley Park

Macclesfield

SK10 4TG

UK

Manoranjan Panda

AstraZeneca India Pvt. Ltd.

Bellary Road, Hebbal

Bangalore 560 024

India

Mauro Pascolutti

Griffith University

Institute for Glycomics

Gold Coast Campus

Queensland 4222

Australia

Laurent Provins

UCB Biopharma

UCB NewMedicines

Global Chemistry

Chemin du Foriest

1420 Braine-L'Alleud

Belgium

Sven Ruf

Sanofi-Aventis Deutschland GmbH

Industriepark Höchst

65926 Frankfurt

Germany

Hartmut Rütten

Sanofi-Aventis Deutschland GmbH

Industriepark Höchst

65926 Frankfurt

Germany

Thorsten Sadowski

Sanofi-Aventis Deutschland GmbH

Industriepark Höchst

65926 Frankfurt

Germany

Herman Schreuder

Sanofi-Aventis Deutschland GmbH

Industriepark Höchst

65926 Frankfurt

Germany

Matthew D. Segall

Optibrium Ltd

7221 Cambridge Research Park

Beach Drive

Cambridge

CB25 9TL

UK

Graham Showell

Taros Chemicals GmbH & Co. KG

Medicinal Chemistry

Emil-Figge-Str. 76a

44227 Dortmund

Germany

Hongmei Song

HitGen Ltd., Floor 7-10

Building B3, Tianfu Life Science Park

No. 88 South Keyuan Road

Chengdu 610041

People's Republic of China

Michael Stocks

The University of Nottingham School of Pharmacy

Centre for Biomolecular Sciences University Park

Nottingham

NG7 2RD

UK

Robin J. Thomson

Griffith University

Institute for Glycomics

Gold Coast Campus

Queensland 4222

Australia

Ronald Tomlinson

AstraZeneca R&D

Discovery Sciences

Chemistry Innovation Centre

35 Gatehouse Drive

Waltham

MA 02451

USA

Jinqiao Wan

HitGen Ltd., Floor 7-10

Building B3, Tianfu Life Science Park

No. 88 South Keyuan Road

Chengdu 610041

People's Republic of China

Alexander Weber

Boehringer Ingelheim Pharma GmbH & Co. KG

Department of Lead Identification and Optimization Support

88397 Biberach an der Riss

Germany

Dirk Weigelt

Karolinska University Laboratory

Special Laboratory for Clinical Pathology/Cytology

14186 Stockholm

Sweden

Bernd Wellenzohn

Boehringer Ingelheim Pharma GmbH & Co. KG

Department of Lead Identificationand Optimization Support

88397 Biberach an der Riss

Germany

Eric Wellner

AstraZeneca R&D

Discovery Sciences

Pepparedsleden 1

431 83 Mölndal

Sweden

Steven S. Wesolowski

AstraZeneca Pharmaceuticals LP

Neuroscience Innovative Medicines

141 Portland St.

Cambridge

MA 02139

USA

Klaus Wirth

Sanofi-Aventis Deutschland GmbH

Industriepark Höchst

65926 Frankfurt

Germany

Andrea Wolkerstorfer

RD&C Research, Development & Consulting GmbH

Neuwaldegger Strasse 35/2/3

A-1170 Vienna

Austria

Xian-Hui Wu

HitGen Ltd., Floor 7-10

Building B3, Tianfu Life Science Park

No. 88 South Keyuan Road

Chengdu 610041

People's Republic of China

Hua Yang

Pharmaron

6 Tai-He Road, BDA

100176 Beijing

People's Republic of China

Preface

In drug discovery, a lead series is a series of related structures (hits or confirmed actives) that display a clear structure–activity relationship (SAR) versus the desired target but still exhibit suboptimal physicochemical, pharmacological, DMPK, toxicological, or intellectual-property-related attributes requiring further chemical modification to improve these liabilities and to deliver a clinical candidate. These chemical modifications most often aid to improve potency, selectivity, pharmacokinetic parameters, or physicochemical properties such as solubility.

Lead generation comprises five basic objectives [1]: (a) validation of structure and purity; (b) definition of a pharmacophore, as such information impacts the strategy for SAR development of the series; (c) selectivity enhancement in order to minimize activity at closely related molecular targets; (d) exclusion of compounds with inappropriate modes of action, such as nonspecific binding to the molecular target; and (e) increase of potency. While hits have often activities in the micromolar range, such compounds need to be optimized toward higher potency as they might be problematic later in development with respect to achieving effective concentrations in the target tissue or organ.

Lead generation [1–5] is the most critical stage in early drug discovery where small-molecule hits stemming from active generation methods are evaluated and undergo limited optimization to identify those promising leads, which then will be subject to more extensive optimization efforts in a subsequent step of drug discovery called lead optimization. Lead generation mainly defines the chemical structures of subsequent clinical candidates [6] and as such is of great importance for the success of a given project.

The drug discovery process generally follows the following path:

The figure depicts the drug discovery process that follows the path: target identification, target validation, active/hit generation, hit to lead phase, lead optimization, preclinial development, and clinical development. Active/hit generation and hit to lead phase are represented as lead generation.

While traditionally the generation of actives has been performed either in analogy to endogenous ligands [7] or by high-throughput screening (HTS) [8], today the medicinal chemist has a wealth of different lead generation methods at hand and lead generation paradigms have changed and evolved constantly. This rather drastic change was the necessary consequence of high attrition rates in the clinic, the escalation of drug development costs beyond the billion dollar mark, and the ever higher expectations of safety and efficacy on the part of regulatory agencies, physicians, and patient populations at large. With an increasing emphasis on translational science and more relevant screening assays, requirements for lead generation chemists have constantly increased as well, difficult drug targets need to be mastered, and hits from phenotypic screens need to be converted into drugs to just name a few of these challenges.

How can a lead generation chemist of today then choose the right active generation methods? How many should be considered and when and what are their advantages and limitations? Which and how many compounds should be screened and which hits should be progressed? How should ancillary techniques like predictive methods, affinity measurements or lead matrices be considered and used? How can the so-called “undrugable” targets, for example, protein–protein interactions or phosphatases be mastered? How can a phenotypic screen outcome be converted into drugs? How can a lead generation chemist be sure that a lead series will be delivering a successful clinical candidate after undergoing the lead optimization phase? All these questions and many more will be discussed and answered in this book by a team of selected, highly experienced lead generation scientists, along with many practical examples of “real-life” learnings.

This volume is organized in six parts, the first of which introduces into the topic of this volume with “learnings from the past” by Mike Hann and an overview on “modern lead generation strategies” by Jörg Holenz, the editor of this volume, and Dean Brown.

In 15 well-elaborated chapters, the following four parts provide the reader with a comprehensive overview of the broad spectrum of methods and strategies currently applied in lead generation projects. The importance of target identification for generating successful leads (Chapters 3 and 4), the broad spectrum of evolving lead generation methods (Chapters 5–11), various approaches to convert hits to successful leads along with ancillary techniques (Chapters 12–16), as well as hypothesis-driven lead generation (Chapter 17) deserve particular mentioning in this context.

The last part exemplifies the above-mentioned methods and strategies in eight impressive success stories on lead structure discovery in many different areas, such as H3 antagonists, PAR-1 antagonists, inhaled ß2-receptor agonists, and cathepsin A inhibitors, or in projects for neglected diseases, to mention a few.

The series editors are grateful to Jörg Holenz for organizing this volume and to work with such excellent authors. Last but not least, we thank Frank Weinreich and Waltraud Wüst from Wiley-VCH Verlag GmbH for their valuable contributions to this project and to the entire book series.

DüsseldorfRaimund Mannhold

Weisenheim am SandHugo Kubinyi

ZürichGerd Folkers

January 2016

References

  1. 1. Michne, W.F. (1996) Hit-to-lead chemistry: a key element in new lead generation. Pharmaceutical News, 3, 19–21.
  2. 2. Bleicher, K.H., Böhm, H.-J., Klaus Müller, K., and Alanine, A.I. (2003) Hit and lead generation: beyond high-throughput screening. Nature Reviews Drug Discovery, 2, 369–378.
  3. 3. Davis, A.M., Keeling, D.J., Steele, J., Tomkinson, N.P., and Tinker, A.C. (2005) Components of successful lead generation. Current Topics in Medicinal Chemistry, 5, 421–439.
  4. 4. Keserü, G.M. and Makara, G.M. (2006) Hit discovery and hit-to-lead approaches. Drug Discovery Today, 11, 741–748.
  5. 5. Hughes, J.P., Rees, S., Kalindjian, S.B., and Philpott, K.L. (2011) Principles of early drug discovery. British Journal of Pharmacology, 162, 1239–1249.
  6. 6. Keserü, G.M. and Makara, G.M. (2009) The influence of lead discovery strategies on the properties of drug candidates. Nature Reviews Drug Discovery, 8, 203–212.
  7. 7. Bosch, F. and Rosich, L. (2008) The contributions of Paul Ehrlich to pharmacology: a tribute on the occasion of the centenary of his Nobel Prize. Pharmacology, 82, 171–179.
  8. 8. Polgar, T. and Keserü, G.M. (2011) Integration of virtual and high throughput screening in lead discovery settings. Combinatorial Chemistry and High Throughput Screening, 14, 1–9.

A Personal Foreword

As drug discovery is fundamentally changing during recent years with an ever-growing emphasis on translation and more disease relevant screening assays, the borders between biology and chemistry become increasingly invisible: chemical biology-driven target identification and concurrent lead generation represent today standard follow-up methods for the increasing number of projects relying on phenotypic screening, while novel drug classes like antibody–drug conjugates close the gap between large biological and small chemical molecules. Today, medicinal chemists play a pivotal part in these multidisciplinary processes by leading and actively shaping them. Lead generation is the area where this evolution is most prominent and has affected a couple of major paradigm changes. It is a crucial discipline where structural properties and liabilities of chemical compounds are defined to a large degree, thus strongly influencing the potential for further optimization toward a successful candidate to test a clinical hypothesis. Lead generation represents one of the most important disciplines for project success, and “shortcuts” in lead generation are often penalized at later stages.

Starting my career in lead optimization and preclinical development, I worked in projects where lead optimization failed to deliver a candidate drug and a renewed lead generation effort was deemed necessary, leading to severe delays and failures to nominate a clinical candidate. This is how I started to gain interest in lead generation and in answering the question how to assure that lead optimization teams would get the lead series quality and choice they need to deliver a successful drug candidate without bigger delays. In the past 6 years, I immersed myself in the wonderful and fascinating world of lead generation. Like no other discipline, lead generation miraculously combines science with technology and creativity. The successful lead generation chemist of today truly works as a discoverer of hitherto unknown targets and at the same time as a creator of leads on the interface between medicinal chemistry and multiple rapidly evolving disciplines such as genetics, biology and pharmacology, or data visualization. Last but not least, she or he must be a “technique aficionado” to embrace all the fascinating ancillary technologies!

I tremendously enjoy working in lead generation and learning all about it, and out of this desire came the idea to write this book together with friends and colleagues from companies and academia, across diverse cultures and backgrounds, but united in the same passion and expertise for this discipline. The book took about 3 years from concept to completion, and I am especially proud to have worked with such a distinguished team of lead generation experts. In my personal view, there is a clear need for an up-to-date reference book covering all aspects of modern applied lead generation. It is my sincere hope that this book may fill this gap and provide a comprehensive answer to “everything you always wanted to know about lead generation!”

I would like to thank the authors for their fantastic contributions and for patiently accommodating all my feedback, the series editors for their trust in me and my concept, the Wiley-VCH team around Frank Weinreich and Waltraud Wüst for the production of this book, and finally my family for being patient with me, when I was spending far too much time on this book than I should as a husband and father.

Cambridge (MA)Jörg Holenz

November 2015

Part I
Introduction to Lead Generation