- Copper-Catalyzed Alkoxycarbonylation of Alkyl Iodides for the Synthesis of Aliphatic Esters: Hydrogen Makes the Difference
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A copper-catalyzed alkoxycarbonylation transformation of unactivated alkyl iodides has been developed. Various alkyl iodides can be converted into the corresponding tert-butyl esters in good yields. NaOtBu acts as both a nucleophile and a base. Moreover, other types of aliphatic esters can also be obtained in moderated yields if extra alcohols are added. Both primary and secondary alkyl alcohols can react successfully.
- Geng, Hui-Qing,Wu, Xiao-Feng
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supporting information
p. 8062 - 8066
(2021/10/25)
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- Selective Construction of C?C and C=C Bonds by Manganese Catalyzed Coupling of Alcohols with Phosphorus Ylides
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Herein, we report the manganese catalyzed coupling of alcohols with phosphorus ylides. The selectivity in the coupling of primary alcohols with phosphorus ylides to form carbon-carbon single (C?C) and carbon-carbon double (C=C) bonds can be controlled by the ligands. In the conversion of more challenging secondary alcohols with phosphorus ylides the selectivity towards the formation of C?C vs. C=C bonds can be controlled by the reaction conditions, namely the amount of base. The scope and limitations of the coupling reactions were thoroughly evaluated by the conversion of 21 alcohols and 15 ylides. Notably, compared to existing methods, which are based on precious metal complexes as catalysts, the present catalytic system is based on earth abundant manganese catalysts. The reaction can also be performed in a sequential one-pot reaction generating the phosphorus ylide in situ followed manganese catalyzed C?C and C=C bond formation. Mechanistic studies suggest that the C?C bond was generated via a borrowing hydrogen pathway and the C=C bond formation followed an acceptorless dehydrogenative coupling pathway. (Figure presented.).
- Liu, Xin,Werner, Thomas
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p. 1096 - 1104
(2020/12/31)
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- Metal-Halogen Exchange-Initiated Intramolecular Conjugate Addition Reactions of Unsaturated Esters
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Intramolecular conjugate addition reactions of internal unstabilized nucleophilic centers formed through rapid lithium-halogen exchange reactions have been used to generate carbocycles from ω-iodo-α,β-unsaturated esters.
- Cooke, Manning P.
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p. 1144 - 1146
(2007/10/02)
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