Diastereo‐ and Enantioselective Synthesis of Organometallic Bis(helicene)s by a Combination of CH Activation and Dynamic Isomerization. Issue 49 (31st October 2013)

• Record Type: Journal Article
• Authors: Shen, Chengshuo; Anger, Emmanuel; Srebro, Monika; Vanthuyne, Nicolas; Toupet, Loïc; Roussel, Christian; Autschbach, Jochen; Réau, Régis; Crassous, Jeanne
• Is Part Of: Chemistry. Volume 19:Issue 49(2013)
• Page Start: 16722
• Page End: 16728
• Publication Date: 2013-10-31
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201302479
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Homochiral and heterochiral <italic>cis</italic>‐bis‐cycloplatinated‐[6]helicene derivatives <bold>1 b^{1, 2}</bold>, as representative examples of platina[6]helicenes that share a common platinum center, have been prepared. A diastereo‐ and enantioselective synthesis, which combines CH activation and dynamic isomerization from heterochiral structure <bold>1 b²</bold> into homochiral structure <bold>1 b¹</bold>, is also described. Overall, this isomerization process results in the transfer of chiral information from one helicene moiety to the other one. The chiroptical properties of homochiral (<italic>P</italic>)‐ and (<italic>M</italic>)‐<bold>1 b¹</bold> were greatly modified upon oxidation into their corresponding (<italic>P</italic>)‐ and (<italic>M</italic>)‐diiodo‐Pt^IV complexes (<bold>5</bold>). The changes were also analyzed by performing theoretical calculations. CH activation in the synthesis of organometallic helicenes is further demonstrated by the preparation of <italic>cis</italic>‐bis‐cycloplatinated‐[8]helicene <bold>1 c</bold>.</p> </abstract>