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• W2083141141 endingPage "236" @default.
• W2083141141 startingPage "219" @default.
• W2083141141 abstract "The preparation of highly diastereo- and enantiomerically enriched planar chiral 1-phenylsulfonyl-substituted tricarbonyl(η5-pentadienyl)iron(1 +) complexes 7 [syn,syn-(1 R,5R)-7 and syn,syn-(1S,5S)-7 (cisoid- or U-forms); de > 99%  5-syn-CH3/5-anti-CH3 ⪢ 100:1, ee > 99%; 87% quant. from resolved 6] is described. Starting from the enantiopure diene (1 E,3 E,S)-5 both enantiomers of the cationic complexes syn,syn-7 become readily accessible via chromatographic resolution of the diastereomeric mixture of the corresponding neutral tricarbonyl(η4-diene)iron(0) complexes 6 [(1 R,5S)-6  ψ-endo-6 and (1 S,5S)-6  ψ-exo-6; de > 99%, ee > 99%; 85% quant. prior to resolution]. The nucleophilic addition of hetero and carbon atom nucleophiles (morpholine, silyl enol ether 8 and silyl ketene acetal 9) to the racemic complex syn,syn-(1 R/S, 5 R/S)-7 afforded the neutral ε-substituted tricarbonyl(η4-diene)iron(0) complexes rac-ψ-exo-10ac in moderate yields [43–68% from syn,syn-(1 R/S,5R/S)-7] as single geometrical isomers [(E,Z) or (E,E); kinetic (U-form/strong nucleophile) or thermodynamic (S-form/less reactive nucleophile) control]. Likewise, nucleophilic addition to the stereochemically homogeneous complexes syn,syn-(1 R,5R)-7 or syn,syn-(1 S,5S)-7 followed by oxidative cleavage of the carbonyl-iron fragment offers an access to ε-substituted dienes 11a-c in moderate to fair yields [45–65%, (E,Z)/(E,E) = > 85:1-1:3] with enantiomeric excesses ranging from > 99%/98.9% [(1 E,3Z,R)-11a/(1 E,3Z,S)-11a] to 93% [(6 E,8 E,S)-11b]. The stereochemistry of the formation and the stereochemical pathways of the nucleophilic addition reactions of the nonracemic complexes syn,syn-7 leading to the dienes 11a-c as well as spectroscopic and structural details are discussed. Furthermore, the reaction proceeds with virtually complete “chirality transfer” from CO via CFe to CN or CC, respectively, with either retention or inversion of stereochemistry of the stereogenic centre with respect to the starting material (S)-1 depending strongly on the reaction conditions. The observed ε-regioselectivity of the nucleophilic addition reaction displays the synthetic equivalence of the cationic complexes of type syn,syn-7 with a planar chiral a6-synthon allowing an umpolung of the classical d6-chemistry." @default.
• W2083141141 created "2016-06-24" @default.
• W2083141141 creator A5013621850 @default.
• W2083141141 creator A5085063768 @default.
• W2083141141 creator A5088754757 @default.
• W2083141141 date "1997-04-01" @default.
• W2083141141 modified "2023-10-15" @default.
• W2083141141 title "“Chirality transfer” in iron-mediated dienylic substitutions via highly enantiomerically enriched planar chiral 1-phenylsulfonyl-substituted tricarbonyl(η5-pentadienyl) iron(1 +) complexes" @default.
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