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N-Carbamate protected amino acid derived guanidine organocatalystsWe report the preparation of a range of N-protected amino acid derived guanidine organocatalysts and their application to the Michael addition of 2-hydroxy-1,4-napthoquinone to β-nitrostyrene, achieving a maximum ee of 26%. Whilst these catalysts gave poor ees, the structural variation together with the X-ray crystallographic study of the intra- and intermolecular hydrogen bonding reported suggest that the C2-symmetric catalyst are lead compounds for the further development of this methodology.
The value of 2 J P–CO as a diagnostic parameter for the structure and thermal reactivity of carbonyl-stabilised phosphonium ylidesA survey of 20 carbonyl-stabilised phosphonium ylides with recently reported X-ray structures shows a strong correlation between the CP to CO torsion angle and the value of 2JP–CO, with high values being associated with an anti configuration and low with syn. Seven new X-ray structural determinations are reported, several for types of ylide not crystallographically characterised before, and these also conform to this pattern. The value of 2JP–CO is then correlated with whether or not thermal extrusion of Ph3PO occurs to give alkynes for over 200 ylides and an empirical rule developed that the extrusion never occurs for ylides where this value is > 11 Hz. This is used to rationalise the anomalous behaviour of some trioxo ylides and cyclic ylides, two of which afford cycloalkynes, isolated after rearrangement as the isomeric 1,3-dienes. The rule also holds for a family of novel highly fluorinated ylides which afford fluorinated alkynes in good yield upon flash vacuum pyrolysis.