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Designing Synthetic Methods and Natural Products Synthesis

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Overman, L. (2024). Designing Synthetic Methods and Natural Products Synthesis. GNT Publishing GmbH. https://doi.org/10.47261/1556
Overman, Larry E.. Designing Synthetic Methods and Natural Products Synthesis. GNT Publishing GmbH, 2024. Book. https://doi.org/10.47261/1556
Overman, L (2024): Designing Synthetic Methods and Natural Products Synthesis, GNT Publishing GmbH, [online] https://doi.org/10.47261/1556

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Designing Synthetic Methods and Natural Products Synthesis

Overman, Larry E.

Lives in Chemistry – Lebenswerke in der Chemie, Vol. 9

(2024)

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About The Author

Larry E. Overman, born in Chicago in 1943, is Distinguished Professor of Chemistry at the University of California, Irvine. He was the recipient of the Arthur C. Cope Award in 2003, and he was awarded the Tetrahedron Prize for Creativity in Organic Chemistry for 2008. Overman's research is focused on the development of new chemical reactions, particularly transition metal catalyzed reactions, and the application of those reactions toward the synthesis of natural products. He is most known for the Overman rearrangement, a Claisen rearrangement of allylic alcohols to give allylic trichloroacetamides.

Abstract

LARRY E. OVERMAN, born in 1943 in Chicago, had joined the newly founded Faculty of Chemistry, University of California, Irvine in 1971. It became his homebase for more than 50 years until his retirement as Distinguished Professor of Chemistry, Emeritus.

How come that he and his wife had chosen Irvine? That over 300 graduate students and postdocs have chosen his lab? That he served also as Chair of the Chemistry Section of the US National Academy of Science, as a founder and consultant in the pharmaceutical industry? Who were his mentors, his professional friends? Why did he early on chase »new chemical reactivity« after his first unexpected discovery? Which of his natural product total syntheses are textbook knowledge today? Who of his students became leaders, even a Nobel Laureate? Larry provides answers.

He managed challenges with impressive rigor and elegance. His students praise him and his unique »Let’s see what happens« and »research is a group endeavor« approach!

l-i-c.org

Table of Contents

Section Title Page Action Price
Lives in Chemistry 3
Published titles in this series 4
Imprint 6
Table of Contents 8
Preface 11
1 Childhood and Education 15
1.1  Family and schooling 17
1.2  Undergraduate studies 24
1.3  Graduate studies 27
1.4  Postdoctoral studies 33
Further Reading 38
2 The 1970s: Early Discoveries 39
2.1  Initiating my research career and the discovery of the Overman rearrangement 41
2.2  Thermal rearrangements 48
2.3  Diels-Alder reactions and the total synthesis of pumiliotoxin C 50
Fashions in Research 52
2.4  Total synthesis of gephyrotoxin and the invention of the aza-Cope Mannich reaction 54
2.5  Catalytic allylic rearrangements 57
2.6  Teaching, mentoring, and life at UC Irvine in the 1970s 58
2.7  Early Participation in Scientific Conferences 62
Further Reading 64
3 The 1980s and 90s: Heterocyclization Reactions 65
3.1  My growing involvement in natural products total synthesis 67
3.2  Iminium ion cyclizations of vinylsilanes and alkynes: synthesis of poison-frog alkaloids 75
3.3  Pinacol-terminated cationic cyclization reactions 80
3.4  Sabbatical in Hannover, Germany, 1985 89
Further Reading 94
4 The 1980s, 90s and 2000s: Pd-Catalyzed Reactions 95
4.1  Intramolecular Heck reactions 97
4.2  Catalytic enantioselective intramolecular Heck reactions 109
Choosing Natural Product Total Synthesis Targets 118
Speculative total synthesis projects 121
4.3  Catalytic enantioselective reactions of alkenes 121
4.4  1993 Was a Special Year 127
Adjusting How to Manage My Research Group 127
Further Reading 129
5 The 1990s and 2000s: Alkaloid Total Synthesis 131
5.1  Tethered Biginelli reactions and guanidinium alkaloids 133
5.2  Sarain A 143
5.3  Epidithiodioxopiperazine (ETP) natural products and tricyclic analogs 150
5.4  Solvent Purification Systems 156
Further Reading 158
6 Fragment Coupling with Tertiary-Carbon Radicals 159
6.1  Investigations of tert-butyl analogs of macfarlandin E 161
6.2  Total synthesis of (-)-aplyviolene: fragment-coupling reactions of tertiary-carbon radicals 165
Further Reading 174
7 Professional Activities 175
7.1 Organic Reactions and Organic Syntheses 177
7.2  U. S. National Academy of Sciences 182
7.3  Industrial associations 184
7.4  Sabbaticals and visiting professorships 187
Further Reading 188
8 Coworkers, Friends, Hobbies, and My Family 189
8.1  Coworkers made it possible and enjoyable 191
8.2  Thoughts on building a research group and mentoring 194
8.3  David MacMillan, 2021 Chemistry Nobel Prize 196
8.4  My choice to remain at UC Irvine for my academic career 198
8.5  Family, friends, recreation and hobbies 201
8.6  Joanne and our family 203
Appendix 207
Afterword 209
Acknowledgement 210
Vita 211
Chemistree 212
Holographs 215
Publications 226
U. S. Patents 244
Links and literature 247
Image sources 249
Index 250
Reactions from our readers 254
Titles in this series 255