Unknown

Dataset Information

0

Wolff Rearrangement of Oxidatively Generated ?-Oxo Gold Carbenes: An Effective Approach to Silylketenes.


ABSTRACT: Gold-catalyzed oxidations of alkynes by N-oxides offer direct access to reactive ?-oxo gold carbene intermediates from benign and readily available alkynes instead of hazardous diazo carbonyl compounds. Despite various versatile synthetic methods developed based on this strategy, one of the hallmarks of ?-oxo carbene/carbenoid chemistry, that is, the Wolff rearrangement, has not been realized in this context. This study discloses the first examples that show the Wolff rearrangement can be readily realized by ?-oxo gold carbenes oxidatively generated from TBS-terminated alkynes (TBS=tert-butyldimethylsilyl). The thus-generated silylketenes can be either isolated pure or subsequently trapped by various internal or external nucleophiles in one pot to afford ?-silylated carboxylic acids, their derivatives, or TBS-substituted allenes.

SUBMITTER: Zheng Y 

PROVIDER: S-EPMC6564687 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

altmetric image

Publications

Wolff Rearrangement of Oxidatively Generated α-Oxo Gold Carbenes: An Effective Approach to Silylketenes.

Zheng Yang Y   Zhang Junqi J   Cheng Xinpeng X   Xu Xinfang X   Zhang Liming L  

Angewandte Chemie (International ed. in English) 20190318 16


Gold-catalyzed oxidations of alkynes by N-oxides offer direct access to reactive α-oxo gold carbene intermediates from benign and readily available alkynes instead of hazardous diazo carbonyl compounds. Despite various versatile synthetic methods developed based on this strategy, one of the hallmarks of α-oxo carbene/carbenoid chemistry, that is, the Wolff rearrangement, has not been realized in this context. This study discloses the first examples that show the Wolff rearrangement can be readil  ...[more]

Similar Datasets

| S-EPMC3983127 | biostudies-other
| S-EPMC6897493 | biostudies-literature
| S-EPMC4090113 | biostudies-literature
| S-EPMC6035048 | biostudies-literature
| S-EPMC3585475 | biostudies-literature
| S-EPMC2902991 | biostudies-literature
| S-EPMC4482412 | biostudies-literature
| S-EPMC8485804 | biostudies-literature
| S-EPMC2847863 | biostudies-literature
| S-EPMC5324612 | biostudies-literature