Diastereoselectivity in the induction of planar chirality in prochiral cymantrenes
摘要:
The carbonylation of the (S)-enantiomer of the palladated derivative of dimethylaminomethylferrocenein the presence of 1,2-bis(hydroxymethyl)cymantrene affords a product containing a chiral plane predominantly of the (R)-configuration. The extent of asymmetric induction amounts to 30-35 %.
Umsetzungen der lithiierten Halbsandwich-Komplexe (CO)3MC5H4Li (M = Mn, Re) mit organischen carbonylverbindungen
摘要:
The reactions of the lithiated half-sandwich complex (CO)(3)MnC5H4-Li([Cym]-Li, 2a) with derivatives of organic dicarboxylic acids have been investigated with the goal of introducing several cymantrenyl ([Cym]) substituents in close proximity into organic molecules. The carboxylic acid chlorides of terephthalic and fumaric acid give, after reaction with excess 2a in THF solution and chromatography of the primary lithium compounds on silica, the bis(dicymantrenylcarbinols), [Cym]C-2(OH)-C6H4-C(OH)[Cym](2) (13a) and E-[Cym]C-2(OH)-CH=CH-C(OH)[Cym](2) (17a) which contain four cymantrenyl units. Phthaloyl chloride produces a product with isobenzofuranol skeleton and three cymantrenyl substituents. Cyclic anhydrides such as maleic and phthalic anhydride lead to lactons containing two geminal cymantrenyl groups.With chloroformates, the lithiated derivatives of cymantrene and cyrhetrene, (CO)(3)MC(5)H(4)-Li (M = Mn (2a), Re (2b)) can be directly converted to tris(cymantrenyl)- and tris(cyrhetrenyl) carbinol, [Cym]C-3-OH (18a) and [Cyr]C-3-OH (18b), respectively. In the presence of paraformaldehyde complexes 2a,b are first converted into the hydroxymethyl compounds (CO)(3)MC(5)H(4)-CH2OH (M = Mn (21a), Re (21b)) which then react, by further lithiation and formaldehyde insertion steps, to give 1,2-bis(hydroxymethyl) half-sandwiches, (CO)(3)MC(5)H(3)(CH2OH)(2)(M = Mn (22a), Re (22b)). Starting from thionyl chloride and 2a, dicymantrenyl sulfoxide, [Cym]2SO (28a), is obtained. The new complexes have been characterized on the basis of their H-1 and C-13 NMR data.