Application of the Nicholas reaction to the synthesis of dicobalt hexacarbonyl complexed diyne ethers

作者：Amin Jahangir; Motevalli Majid; Richards Christopher J^*

来源：Journal of Organometallic Chemistry, 2015, 776: 43-50.

DOI：10.1016/j.jorganchem.2014.10.030

• Alkynes
• Cobalt
• Ethers
• Cations
• Diastereoselective

Addition of propargylic or homopropargylic ynols to dicobalt hexacarbonyl propargylium cations gave the expected ether products of the Nicholas reaction, with the exception of 4-phenyl-3-butyn-1-ol which gave a dihydrofuran due to propargylium cation promoted 5-endo ring-closure. Use of chiral dicobalt hexacarbonyl complexed propargylic ynols as both propargylium cation precursor and nucleophile gave racemic doubly complexed disymmetric diyne ethers, each as a single diastereoisomer. Addition of dicobalt hexacarbonyl complexed 1-phenyl-1-butyne-3-ene to the propargylium cation derived from dicobalt hexacarbonyl complexed 1-phenyl-1-butyn-3-ol, followed by the addition of a nucleophile (NuH), gave double complexed 1,7-diphenyl-3-Nu-5-methylhepta-1,6-diynes (d.r. > 10:1).

• 出版日期2015-1-15