π-Complexes with planar chirality: control centres for stereoselective synthesis

Organom etallic π-complexes are defined as the synthetic equivalents of cationic synthons for use in organic synthesis. W hen complexes of this type are employed, activation and stereocontrol effects (which arise from properties of the metal), and regiocontrol effects and functional group locations (resulting from substitution pattern), are separated from one another. The consequences of this distinction for synthesis design are discussed by using two examples, an approach for the synthesis of tridachiapyrones based on a ‘linear’ synthetic sequence, and an alternative method for double alkylations employing an ‘iterative’ strategy. Access to resolved compounds for enantiom er synthesis is described.

[1]  G. Stephenson,et al.  Transition-metal mediated asymmetric synthesis. Part 5. Alternative methods for the formation of tricarbonyl(η5-cyclohexadienyl)iron(1+) salts , 1987 .

[2]  D. W. Ribbons,et al.  Aromatic biotransformations 2: production of novel chiral fluorinated 3,5-cyclohexadiene--1,2-diol-1-carboxylates , 1987 .

[3]  S. Ley,et al.  Microbial oxidation in synthesis: A six step perparation of (+)-pinitol from benzene , 1987 .

[4]  G. Stephenson,et al.  Reversal of regiocontrol in the alkylation of an arene π-complex , 1986 .

[5]  S. Greenfield,et al.  Functionalisation of 1,3-dienes using cationic complexes of molybdenum , 1985 .

[6]  P. Williard,et al.  Addition of Grignard reagents and ketone enolates to the arene in (arene)manganese tricarbonyl cations , 1982 .

[7]  G. Stephenson Transition-metal mediated asymmetric synthesis. Part 3. Preparation and stereospecific alkylation of unsymmetrically substituted tricarbonyl(cyclohexadienyl)iron(1+) salts: an organometallic approach to the synthesis of carvone, cryptomerion, and bilobanone , 1982 .

[8]  A. Birch,et al.  Optically active tricarbonyl(cyclohexadienyl)iron(1+) salts: Synthetic equivalents to spatially directed organic cations , 1981 .

[9]  J. Mckennis,et al.  The importance of reaction conditions in the use of the (η5-cyclohexadienyl)tricarbonyliron cation in organic synthesis , 1981 .

[10]  A. J. Pearson,et al.  Stereocontrolled approaches to substituted tetrahydrofuran and cis-hydrindene derivatives via cyclohexadiene-Fe(CO)3 complexes☆ , 1980 .

[11]  A. J. Pearson Organoiron complexes in organic synthesis. Part 2. Conformational and steric effects of methyl substituents in tricarbonyliron derivatives of bicyclo[4.4.0]decadienes , 1978 .

[12]  A. J. Pearson A novel approach to the formation of quaternary centres and the introduction of angular substituents by using tricarbonyldieneiron complexes , 1977 .

[13]  P. Pauson,et al.  Preparation and reactivity of (η-arene)tricarbonylmanganese cations bearing functional substituents , 1975 .