New avenues in the directed deprotometallation of aromatics: recent advances in directed cupration
Recent advances in the selective deprotometallation of aromatic reagents using alkali metal cuprates are reported. The ability of these synergic bases to effect deprotonation under the influence of a directing group is explored in the context of achieving new and more efficient organic transformatio...
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| Published in | Dalton transactions : an international journal of inorganic chemistry Vol. 43; no. 38; pp. 14181 - 1423 |
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| Main Authors | , , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
Royal Society of Chemistry
14.10.2014
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| Subjects | |
| Online Access | Get full text |
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| Summary: | Recent advances in the selective deprotometallation of aromatic reagents using alkali metal cuprates are reported. The ability of these synergic bases to effect deprotonation under the influence of a directing group is explored in the context of achieving new and more efficient organic transformations whilst encouraging greater ancillary group tolerance by the base. Developments in our understanding of the structural chemistry of alkali metal cuprates are reported, with both Gilman cuprates of the type R
2
CuLi and Lipshutz and related cuprates of the type R
2
Cu(X)Li
2
(X = inorganic anion) elucidated and rationalised in terms of ligand sterics. The generation of new types of cuprate motif are introduced through the development of adducts between different classes of cuprate. The use of DFT methods to interrogate the mechanistic pathways towards deprotonative metallation is described. Theoretical modelling of
in situ
rearrangements undergone by the cuprate base are discussed, with a view to understanding the relationship between R
2
CuLi and R
2
Cu(X)Li
2
, their interconversion and the implications of this for cuprate reactivity. The advent of a new class of adduct between different cuprate types is developed and interpreted in terms of the options for expelling LiX from R
2
Cu(X)Li
2
. Applications in the field of medicinal chemistry and (hetero)arene derivatization are explored.
Advances in directed aromatic deprotometallation are reported in the context of recent developments in our understanding of lithium cuprates. |
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| Bibliography: | Andrew Peel completed his degree in Natural Sciences at the University of Cambridge in 2013. He is currently undertaking a PhD in Chemistry in the Wheatley group. His research presently focuses on lithium amidocuprate chemistry, with his principal interests being in chemical crystallography. His other interests include growing exotic chilli peppers and playing guitar. Ryo Takita obtained his PhD in 2006 from the University of Tokyo with Prof. Masakatsu Shibasaki. From 2006 to 2007, he worked as a postdoctoral Fellow at Massachusetts Institute of Technology with Professor Timothy M. Swager. He became an Assistant Professor at Kyoto University (2007-2010) and University of Tokyo (2010-2012), and was promoted to Lecturer (2012-2014). He is currently a Deputy Team Leader at RIKEN Center for Sustainable Resource Science (CSRS). His research interests include organic chemistry for unexplored reactivity and functions. Masanobu Uchiyama obtained his PhD in 1998 from the University of Tokyo with Prof. Koichi Shudo. He worked as an Assistant Professor at Tohoku University (1995-2001) and University of Tokyo (2001-2003), and was promoted to lecturer (2003-2006). He became Associate Chief Scientist at RIKEN in 2006. He is currently a Full Professor at the University of Tokyo (from 2010) and Chief Scientist/Team Leader at RIKEN and RIKEN CSRS (from 2013). His research interests are in the area of synthetic organic chemistry with an emphasis on organometallic, physical, and computational chemistry. Philip Harford obtained an MSc degree in Natural Sciences in 2008 from the University of Cambridge and is currently studying for his PhD there under the supervision of Dr Andrew Wheatley. His research is focussing on the synthesis of heterobimetallic lithium cuprate bases with particular interest in their structures as derived from X-ray crystallographic studies. Florence Mongin obtained her PhD in Chemistry in 1994 from the University of Rouen (France) under the supervision of Prof. Guy Queguiner. After two years at the Institute of Organic Chemistry of Lausanne (Switzerland) as a postdoctoral Fellow with Prof. Manfred Schlosser, she returned to the University of Rouen as an Assistant Professor in 1997 (HDR in 2003). She took up her present position in 2005 as Professor at the University of Rennes (France) and was appointed Junior Member of the Institut Universitaire de France in 2009. Her interests include the functionalization of aromatic compounds including heterocycles with recourse to mixed lithium-metal bases. Floris Chevallier is an Associate Professor at the University of Rennes 1 (Rennes, France). He studied (organic) chemistry at the universities of Orléans and Nantes. He received his PhD in 2004 under the supervision of Prof. Jean-Paul Quintard, for whom he worked on organotin chemistry. In 2005, he joined the group of Prof. Bernhard Breit at the Albert-Ludwigs-Universität Freiburg (Freiburg, Germany) as a postdoctoral researcher, where he focused on supramolecular catalysis. His current research interests include organometallic methodologies and molecular self-assemblies. Andrew Wheatley obtained his BSc from the University of Kent at Canterbury in 1995. He then worked at Cambridge under the guidance of Dr Ron Snaith, receiving his PhD in 1999 and an MA (Cantab) in 2002. After his PhD studies he undertook a Research Fellowship at Gonville & Caius College before becoming a University Lecturer at Cambridge (2000) and a Fellow of Fitzwilliam College. He has received the Harrison Memorial Medal from the RSC and more recently he has been a Visiting Associate Professor at Tohoku University, Japan. He is now a University Senior Lecturer at Cambridge. ObjectType-Article-2 SourceType-Scholarly Journals-1 ObjectType-Feature-3 content type line 23 ObjectType-Review-1 ObjectType-Article-1 ObjectType-Feature-2 |
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c4dt01130a |