Cydopropanation enantioselective

The Rh2(DOSP)4 catalysts (6b) of Davies have proven to be remarkably effective for highly enantioselective cydopropanation reactions of aryl- and vinyl-diazoacetates [2]. The discovery that enantiocontrol could be enhanced when reactions were performed in pentane [35] added advantages that could be attributed to the solvent-directed orientation of chiral attachments of the ligand carboxylates [59]. In addition to the synthesis of (+)-sertraline (1) [6], the uses of this methodology have been extended to the construction of cyclopropane amino acids (Eq. 3) [35], the synthesis of tricyclic systems such as 22 (Eq. 4) [60], and, as an example of tandem cyclopropanation-Cope rearrangement, an efficient asymmetric synthesis of epi-tremulane 23 (Eq. 5) [61]. 

In 1994, asymmetric cydopropanation (ACP) with ruthenium catalysts was first reported by Nishiyama and coworkers [ 19,20] by adoption of their chiral bis(oxazolinyl)pyridine (Pybox) ligands. The reaction profiles of Ru Pybox catalysts reveal extremely high trans selectivity with high enantioselectivity (or di-astereoselectivity) of cyclopropane products at the relatively low reaction temperatures (around 20-50 °C) so far reported for ruthenium catalysts. After 1997,... 

Soluble, poly(ethylene glycol)-supported bisoxazolines were used as ligands for enantioselective Diels-Alder as well as cydopropanation and ene reactions (11) [21]. 

A Cu-Box complex supported on monolith (51) was developed for the enantio-selective cydopropanation of ethyl diazoacetate. The flow reactions using (51) provided an increase in enantioselectivities of about 20% relative to those for the homogenous batch process (Scheme 7.38) [142]. Pyridine-oxazolidine based monoliths (52) and (53), whose central metals were Ru and Cu, respectively, were also developed [143,144]. Mesoporous silica was utilized as a support for the Cu-Box complex for asymmetric cydopropanation in a flow reador. Aza(bisoxazoline) was easily immobilized on siliceous mesocellular foam MCF) microparticles, which are... 

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