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Mixed s-block metal organometallic reagents have been successfully utilised in the catalytic intramolecular hydroalkoxylation of alkynols. This success has been attributed to the unique manner in which these reagents can overcome the challenges of the reaction: namely OH activation and coordination to and then addition across a C[triple bond, length as m-dash]C bond. In order to optimise the reaction conditions and to garner vital catalytic system requirements, a series of alkali metal magnesiates were enlisted for the catalytic intramolecular hydroalkoxylation of 4-pentynol. In a prelude to the main investigation, the homometallic magnesium dialkyl reagent MgR 2 (where R = CH 2 SiMe 3 ) was utilised. This reagent was unsuccessful in cyclising the alcohol into 2-methylenetetrahydrofuran 2a or 5-methyl-2,3-dihydrofuran 2b , even in the presence of multidentate Lewis donor molecules such as N , N , N ', N '', N ''-pentamethyldiethylenetriamine (PMDETA). Alkali metal magnesiates M I MgR 3 (when M I = Li, Na or K) performed the cyclisation unsatisfactorily both in the absence/presence of N , N , N ', N '-tetramethylethylenediamine (TMEDA) or PMDETA. When higher-order magnesiates ( i.e. , M I  2 MgR 4 ) were employed, in general a marked increase in yield was observed for M I = Na or K; however, the reactions were still sluggish with long reaction times (22-36 h). A major improvement in the catalytic activity of the magnesiates was observed when the crown ether molecule 15-crown-5 was combined with sodium magnesiate Na 2 MgR 4 (TMEDA) 2 furnishing yields of 87% with 2a  :  2b ratios of 95 : 5 after 5 h. Similar high yields of 88% with 2a  :  2b ratios of 90 : 10 after 3 h were obtained combining 18-crown-6 with potassium magnesiate K 2 MgR 4 (PMDETA) 2 . Having optimised these systems, substrate scope was examined to probe the range and robustness of 18-crown-6/K 2 MgR 4 (PMDETA) 2 as a catalyst. A wide series of alkynols, including terminal and internal alkynes which contain a variety of potentially reactive functional groups, were cyclised. In comparison to previously reported monometallic systems, bimetallic 18-crown-6/K 2 MgR 4 (PMDETA) 2 displays enhanced reactivity towards internal alkynol-cyclisation. Kinetic studies revealed an inhibition effect of substrate on the catalysts via adduct formation and requiring dissociation prior to the rate limiting cyclisation step.

s-Block cooperative catalysis: alkali metal magnesiate-catalysed cyclisation of alkynols