125641-94-3Relevant academic research and scientific papers
The first palladium-catalyzed Sonogashira coupling of unactivated secondary alkyl bromides
Altenhoff, Gereon,Würtz, Sebastian,Glorius, Frank
, p. 2925 - 2928 (2006)
A palladium-carbene catalyzed Sonogashira coupling of unactivated alkyl bromides with alkyl substituted alkynes is reported. For the first time, unactivated secondary alkyl halides were successfully employed in Sonogashira reactions.
Iron-catalyzed Suzuki-Miyaura coupling reaction of unactivated alkyl halides with lithium alkynylborates
Nakagawa, Naohisa,Hatakeyama, Takuji,Nakamura, Masaharu
, p. 486 - 488 (2015/05/27)
A Suzuki-Miyaura coupling reaction between unactivated alkyl halides and lithium alkynylborates was performed using an iron-bisphosphine catalyst. The reaction shows high chemoselectivity and is applicable to a broad scope of substrates bearing electrophilic functional groups. A radical probe experiment using cyclopropylmethyl bromide was conducted to investigate the nature of the intermediate in the reaction, showing that an alkyl radical species is generated from the alkyl halide substrate.
Nickel-catalyzed sonogashira reactions of non-activated secondary alkyl bromides and iodides
Yi, Jun,Lu, Xi,Sun, Yan-Yan,Xiao, Bin,Liu, Lei
supporting information, p. 12409 - 12413 (2013/12/04)
A nicked reaction: The title reaction of terminal alkynes with non-activated secondary alkyl iodides and bromides was accomplished for the first time. This reaction provides a new and practical approach for the synthesis of substituted alkynes (see scheme; cod=cyclo-1,5-octadiene). Copyright
Vinylic Organoboranes. 4. A General, One-Pot Synthesis of 6- and 7-Alkyn-1-ols via Boracyclanes. Influence of Steric Effects in the Iodination of Lithium Alkynyl "Ate" Complexes of Dialkylborinates
Brown, Herbert C.,Basavaiah, D.,Bhat, N. G.
, p. 4518 - 4521 (2007/10/02)
The iodination of the "ate" complexes derived from various B-alkoxyborinane derivatives and 1-alkynyllithium has been investigated.The results indicate the ate complex from B-methoxyborinane is converted into desired 6-alkyn-1-ol in a yield of only 22percent, with much larger amounts, 65percent, of the undesired 1-iodo-1-alkyne.Increases in the steric bulk of the alkoxy group on boron increase the yield of the required 6-alkyn-1-ol with the best results realized with B-(triphenylmethoxy)borinane.Treatment of B-(triphenylmethoxy)borinane with 1-alkynyllithium affords the corresponding "ate" complex.Subsequent iodination induces the migration of one end of the cycloalkyl chain from boron to the adjacent carbon, resulting in the formation of the one-carbon homologated borepane moiety.This then undergoes a rapid deiodoboronation to afford the corresponding (6-alkyn-1-yl)boronate ester.Oxidation of these esters produces the desired 6-alkyn-1-ols in excellent yields (85percent).An attempt to extend this reaction to di-n-alkylborinates to prepare the corresponding unsymmetrical alkynes did not achieve satisfactory results.Alternatively, the iodination of the "ate" complex from B-methylborinane and 1-alkynyllithium, followed by oxidation, provides the required 6-alkyn-1-ols in high yields.This procedure has been successfully extended to the seven-membered borepane moiety to provide the corresponding 7-alkyn-1-ols.Extension of this reaction to the di-n-alkylmethylboranes provides the corresponding unsymmetrical alkynes in good yields.Thus, these procedures constitute a simple, general and one-pot synthesis of the desired alkyn-1-ols, valuable synthons in organic synthesis.Insect pheromones, (Z)-7-tetradecenaland (Z)-7-hexadecenal, were readily prepared in excellent yields by utilizing this convenient procedure.
