Electron-transfer reduction of selected alcohols with alkalide K−, K+(15-crown-5)2 via organometallic intermediates

Stepwise Two-Electron-Transfer Reduction of Cyclic Ethers and Lactones with Alkalide K-, K+(15-Crown-5)2

“…Results of our works [26][27][28][29][30] allow us to propose a general mechanism of the stepwise two-electron-transfer from the potassium anion to a cyclic ether (Scheme 3). This process occurs exclusively according to path B (Scheme 1) via path b 1 or b 2 ; path a is not observed.…”

“…The discussion presented in this review is based on a series of seven works describing behavior of some cyclic ethers [26][27][28][29][30] and lactones [31,32].…”

“…Another example is the reaction of K with potassium glycidoxide (Scheme 6) [28]. Substrate radical anion 16 is formed after the first electron transfer to the LUMO localized on the oxirane ring.…”

Electron-Transfer Processes Mediated by Alkalides: A Critical Approach

“…Alcohols and alkoxides can be efficiently reduced with K − , K + (15C5) 2 [82]. A simple alcohol 30 (Scheme 11), e.g.…”

2 Alkali and alkaline-earth metals

“…69 The structure of the vinyl ether was shown to determine the direction of the C-O bond cleavage by [K][K(15-crown-5) 2 ] to give various potassium alkoxides 70 and the mechanism of the reactions of the potasside with methanol, propanol and glycidol has been investigated. 71 The synthesis and structure of the triphosphaallyl compound [KP 3 (SiBu t 3 ) 2 (thf) 2 ] 2 have appeared. 72 The preparation and structure of [Rb(m-OCH 2 Bu t ) 4 (py)Ti(OCH 2 Bu t )] 2 , [Rb(m-dmp)Ti(dmp) 4 ] ' and [Rb(m-dmp) 2 (m-OCH 2 Bu t ) 2 Ti(OCH 2 Bu t )] ' have been reported as potential precursors for chemical vapour deposition of ceramic oxides.…”