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A DFT calculation-inspired Rh(i)-catalyzed reaction via suppression of ?-H shift in ?-alkyldiazoacetates.

ABSTRACT: Metal-associated carbenes from diazo compounds promote many useful chemistry transformations in modern organic chemistry. However, compared to ?-aryldiazoacetate-derived carbenes (ArDCs), the synthetic application of ?-alkyldiazoacetate-derived carbenes (AlDCs) is greatly limited due to intramolecular ?-H transfer (elimination) that results in alkenes as the main by-products. An intriguing ?-alkyldiazoacetate-involved three-component reaction has been developed following DFT calculation inspiration to provide ?-hydroxyl ?-alkyl-?-amino acid derivatives in good yields. The intramolecular ?-H shift of an ?-alkyldiazoacetate-derived carbene was successfully suppressed by the association of a Rh(i) complex to form the corresponding active ammonium ylide, which was trapped before the fast 1,2-H transfer process. A Rh(i)-chiral diene complex was identified as an effective catalyst to give an asymmetric version of the reaction with good enantioselectivity. This reaction provides insight into extending the efficient transformation of ?-alkyldiazoacetate-derived carbenes and their synthetic application.

SUBMITTER: Liu S 

PROVIDER: S-EPMC5635810 | biostudies-other | 2017 Jun

REPOSITORIES: biostudies-other

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A DFT calculation-inspired Rh(i)-catalyzed reaction <i>via</i> suppression of α-H shift in α-alkyldiazoacetates.

Liu Shunying S   Jiang Jun J   Chen Jianghui J   Wei Qinghua Q   Yao Wenfeng W   Xia Fei F   Hu Wenhao W  

Chemical science 20170322 6

Metal-associated carbenes from diazo compounds promote many useful chemistry transformations in modern organic chemistry. However, compared to α-aryldiazoacetate-derived carbenes (ArDCs), the synthetic application of α-alkyldiazoacetate-derived carbenes (AlDCs) is greatly limited due to intramolecular α-H transfer (elimination) that results in alkenes as the main by-products. An intriguing α-alkyldiazoacetate-involved three-component reaction has been developed following DFT calculation inspirat  ...[more]

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