More Dead Ends and Detours (eBook)

Miguel A. Sierra studied chemistry at the Universidad Complutense de Madrid (UCM), receiving his PhD in 1987, after which he was appointed Assistant Professor. After a postdoctoral stay at Colorado State University under Louis Hegedus, he returned to Madrid where he became associate professor in 1990 and full professor in 2005. His research encompasses Organic Synthesis and mechanistic studies using transition metal compounds, bio-organometallic chemistry, the development of chelating agents for phyto-remediation and the design and synthesis of new energetic materials. Professor Sierra has been the secretary of Organic Division of the Spanish Chemical Society, a member of its board, and a member of the Scientific Advisory Board for the Organization for the Prohibition of Chemical Weapons (OPCW). He has published around 170 scientific articles, 4 books and 5 patents. Maria C. de la Torre studied chemistry at the Universidad Complutense de Madrid (UCM) where she received her PhD in 1986. After a postdoctoral stay at Imperial College under Steven Ley and Colorado State University under Albert Meyers, she returned to Madrid in 1989 as a scientific researcher at the Consejo Superior de Investigaciones Científicas. At present she is a staff member of the Synthesis, Structure and Properties of Organic Compounds Department, at the Instituto de Química Orgánica General (IQOG). Her current research interests focus on the chemistry of densely functionalized natural products, the preparation of natural product hybrids with mixed and/or complementary biological properties, and the development of synthetic strategies to the building of metal-based natural product macrocycles. Fernando P. Cossío studied Chemical Science at the University of Zaragoza and went on to receive a PhD in 1986 at the University of the Basque Country (UPV/EHU). He has spent post-doctoral fellowships at the Centre National de la Recherche Scientifique under Dr. Jean-Paul Picard in Talence (France) and at the University of California Los Angeles under Kendall N. Houk. He became an Associate Professor at the UPV/EHU Faculty of Chemistry in 1988 and a full Professor of this University in 2002. He has occupied a number of posts, such as the dean of the UPV/EHU Faculty of Chemistry, vice-chancellor of Research and International Relations at the UPV/EHU (2001-2004), and president of the Executive Committee of Ikerbasque, the Basque foundation for science (2009-). His current research interests focus on the study of pericyclic and C-C bond forming reactions by computational and experimental methods.

PREFACE

INTRODUCTION
Intermediate in the Total Synthesis of Brevetoxin A

THE INERTIA OF CONVENTIONAL FUNCTIONAL GROUPS
Welwitindolinone A Isonitrile
'Overprotecting-Maverick' Protecting Groups

THE DIELS - ALDER REACTION
(-)-Platensimycin 40
Stephacidins A and B 49

THE ALDOL CONDENSATION 61
The ABC Ring Moiety of (-)-Norzoanthamine
(+)-TMC-151C 71

CYCLIZATIONS: CONCERTED, RADICAL, OR POLAR?
(±)-Merrilactone A
(-)-Pseudolaric Acid B
Formal Synthesis of Platensimycin

MACROCYCLES: FROM RELUCTANT RING CLOSURE TO RELUCTANT RING OPENING
Ustiloxin D
Largazole

STEREOCHEMISTRY, CONTROLLED OR UNCONTROLLED?
(-)-Samaderin Y
(±)-Lyconadin A
Vannusal B

TRANSITION METAL-MEDIATED TRANSFORMATIONS VS 'CONVENTIONAL' REACTIONS
Blumiolide C
Arylomycin A2
(-)-Strychnine

WHEN METATHESIS FAILS
(+)-Saxitoxin
Laulimalide Family

OXIDATIONS IN C - C BOND BUILDING
Cortistatins A and J
Gambierol ABC Moiety

THE FAILURE OF EPOXIDE RING OPENING AND THE LIMITS OF CASCADE REACTIONS
C_D_E_F_ Domain of Maitotoxin