935753-18-7Relevant academic research and scientific papers
Copper-catalyzed enantioselective allylic substitution with readily accessible carbonyl- and acetal-containing vinylboron reagents
Gao, Fang,Carr, James L.,Hoveyda, Amir H.
supporting information; experimental part, p. 6613 - 6617 (2012/08/14)
More with boron: The title reaction was developed to generate quaternary carbon stereogenic centers through the use of commercially available vinylboron reagents (see scheme, MOM=methoxymethyl, NHC=N-heterocyclic carbene, pin=pinacolato). Application of t
Synthesis of quaternary carbon stereogenic centers through enantioselective Cu-catalyzed allylic substitutions with vinylaluminum reagents
Gao, Fang,McGrath, Kevin P.,Lee, Yunmi,Hoveyda, Amir H.
supporting information; experimental part, p. 14315 - 14320 (2010/12/19)
Catalytic enantioselective allylic substitution (EAS) reactions, which involve the use of alkyl- or aryl-substituted vinylaluminum reagents and afford 1,4-dienes containing a quaternary carbon stereogenic center at their C-3 site, are disclosed. The C-C bond-forming transformations are promoted by 0.5-2.5 mol % of sulfonate bearing chiral bidentate N-heterocyclic carbene (NHC) complexes, furnishing the desired products efficiently (66-97% yield of isolated products) and in high site (>98% SN2′)- and enantioselectivity [up to 99:1 enantiomer ratio (er)]. To the best of our knowledge, the present report puts forward the first cases of allylic substitution reactions that result in the generation of all-carbon quaternary stereogenic centers through the addition of a vinyl unit. The aryl- and vinyl-substituted vinylaluminum reagents, which cannot be prepared in high efficiency through direct reaction with diisobutylaluminum hydride, are accessed through a recently introduced Ni-catalyzed reaction of the corresponding terminal alkynes with the same inexpensive metal-hydride agent. Sequential Ni-catalyzed hydrometalations and Cu-catalyzed C-C bond-forming reactions allow for efficient and selective synthesis of a range of enantiomerically enriched EAS products, which cannot be accessed by previously disclosed strategies (due to inefficient vinylmetal synthesis or low reactivity and/or selectivity with Si-substituted derivatives). The utility of the protocols developed is demonstrated through a concise enantioselective synthesis of natural product bakuchiol.
