Asymmetric Tricarbonyliron Complexation of Cyclohexadiene Directed by Chiral Ester and Amide Auxiliaries

Ong, Chi Wi; Huang, Chih‐Feng; Chang, Tsu Hsing

doi:10.1021/om960376e

Cited by 9 publications

References 9 publications

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Enantioselective Synthesis of cis‐Decalins by Merging the Birch Reduction and Inverse‐Electron‐Demand Diels–Alder Reaction

Shi

Wang

et al. 2023

Angewandte Chemie

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Herein, we show that the combination of the Birch reduction of readily available anisole derivatives and the catalytic asymmetric inverse-electron-demand Diels-Alder reaction of 2-pyrones can serve as a powerful platform for the diverse synthesis of synthetically important cis-decalin scaffolds. Enabled by a wellmodified chiral bis(oxazoline) ligand/Cu II complex, a wide range of polysubstituted cis-decalin scaffolds with up to six contiguous stereocenters were generated efficiently. The synthetic potential of this method is demonstrated by the concise synthesis of the sesquiterpene (+)-occidentalol and a key intermediate for seven triterpenes. Mechanistic studies suggest the 1,3-cyclohexadienes formed in situ are the key intermediates, and efficient kinetic resolution occurs when C2-and/or C3substituted 1,4-cyclohexadienes are utilized as substrates. DFT calculations elucidated that the Diels-Alder reaction proceeds in a stepwise fashion and revealed the origins of the stereoselectivities.

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Enantioselective Synthesis of cis‐Decalins by Merging the Birch Reduction and Inverse‐Electron‐Demand Diels–Alder Reaction

Shi

Wang

et al. 2023

Angewandte Chemie

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Enantioselective Synthesis of cis‐Decalins by Merging the Birch Reduction and Inverse‐Electron‐Demand Diels–Alder Reaction

Shi

Wang

et al. 2023

Angew Chem Int Ed

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Herein, we show that the combination of the Birch reduction of readily available anisole derivatives and the catalytic asymmetric inverse‐electron‐demand Diels–Alder reaction of 2‐pyrones can serve as a powerful platform for the diverse synthesis of synthetically important cis‐decalin scaffolds. Enabled by a well‐modified chiral bis(oxazoline) ligand/CuII complex, a wide range of polysubstituted cis‐decalin scaffolds with up to six contiguous stereocenters were generated efficiently. The synthetic potential of this method is demonstrated by the concise synthesis of the sesquiterpene (+)‐occidentalol and a key intermediate for seven triterpenes. Mechanistic studies suggest the 1,3‐cyclohexadienes formed in situ are the key intermediates, and efficient kinetic resolution occurs when C2‐ and/or C3‐substituted 1,4‐cyclohexadienes are utilized as substrates. DFT calculations elucidated that the Diels–Alder reaction proceeds in a stepwise fashion and revealed the origins of the stereoselectivities.

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Chiral Alkoxy Side Chains from (‐)‐Amino Acids in Mediating Asymmetric Synthesis of Tricarbonyl(cyclohexadienyl)iron Complexes

Chang¹,

Kuo²,

Ong³

1997

J Chinese Chemical Soc

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The asymmetric induction in the complexation reaction of (S)‐1‐methyl‐2‐(5‐methyl‐cyclohexa‐1,4‐dienylmethyloxy)‐pyrrolidine 5 and (S)‐2‐(2‐N,N‐dimethylamino‐1‐propanoxy)‐5‐methylcyclohexa‐1,4‐diene 6 having heteroatom adjacent the stereogenic center has been investigated. The diastereoselectivity was determined directly from the diastereotopic peaks in the 1H NMR or by chemical correlation with 9. The conversion of η‐1,4‐complexes 7a and 8a to 9 proceeded with high retention of configuration while that of the η‐2,5‐Fe(CO)3 complexes 7b and 8b undergoes considerable racemization.

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Asymmetric Tricarbonyliron Complexation of Cyclohexadiene Directed by Chiral Ester and Amide Auxiliaries

Cited by 9 publications

References 9 publications

Enantioselective Synthesis of cis‐Decalins by Merging the Birch Reduction and Inverse‐Electron‐Demand Diels–Alder Reaction

Enantioselective Synthesis of cis‐Decalins by Merging the Birch Reduction and Inverse‐Electron‐Demand Diels–Alder Reaction

Enantioselective Synthesis of cis‐Decalins by Merging the Birch Reduction and Inverse‐Electron‐Demand Diels–Alder Reaction

Chiral Alkoxy Side Chains from (‐)‐Amino Acids in Mediating Asymmetric Synthesis of Tricarbonyl(cyclohexadienyl)iron Complexes

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