Catalytic asymmetric dearomatization(CADA)has emerged as a powerful strategy for transforming planar aromatic systems into three-dimensional chiral architectures[1].Notably,the Büchner reaction and arene cyclopro...Catalytic asymmetric dearomatization(CADA)has emerged as a powerful strategy for transforming planar aromatic systems into three-dimensional chiral architectures[1].Notably,the Büchner reaction and arene cyclopropanation excel in constructing complex polycyclic frameworks[2].However,current methods predominantly rely on diazo compounds as carbene precursors(Scheme1a),which pose safety risks and limit functional group compatibility.展开更多
A variety of metal coordination modes that may provide carbon-carbon bond cleavage pathways in benzene and benzenoid hydrocarbons are summarized in a rubric.Some of these are evident in recently published work,and oth...A variety of metal coordination modes that may provide carbon-carbon bond cleavage pathways in benzene and benzenoid hydrocarbons are summarized in a rubric.Some of these are evident in recently published work,and others represent challenges for future research.The first category includes thermolyses and ring opening metathesis polymerization of iridium η^(4)adducts.aluminum(l)additions that first yield η_(3)^(2)1,2-or 1,4 adducts,intramolecular C=C metatheses that involve initial 1,2 Mo=C additions,multimetallic activation via dititaniumη³binding modes,and a one-off lutetium mediated process that defies simple classification.However,few of these transformations are currently catalytic.The interpretation of most has been aided by DFT calculations,and related lines of investigation are briefly treated.展开更多
文摘Catalytic asymmetric dearomatization(CADA)has emerged as a powerful strategy for transforming planar aromatic systems into three-dimensional chiral architectures[1].Notably,the Büchner reaction and arene cyclopropanation excel in constructing complex polycyclic frameworks[2].However,current methods predominantly rely on diazo compounds as carbene precursors(Scheme1a),which pose safety risks and limit functional group compatibility.
基金the US National Science Foundation(NSFCHE-1900549),Welch Foundation(A-2189)Alexander von Humboldt Foundation for support,and many of the profiled investigators for helpful comments.
文摘A variety of metal coordination modes that may provide carbon-carbon bond cleavage pathways in benzene and benzenoid hydrocarbons are summarized in a rubric.Some of these are evident in recently published work,and others represent challenges for future research.The first category includes thermolyses and ring opening metathesis polymerization of iridium η^(4)adducts.aluminum(l)additions that first yield η_(3)^(2)1,2-or 1,4 adducts,intramolecular C=C metatheses that involve initial 1,2 Mo=C additions,multimetallic activation via dititaniumη³binding modes,and a one-off lutetium mediated process that defies simple classification.However,few of these transformations are currently catalytic.The interpretation of most has been aided by DFT calculations,and related lines of investigation are briefly treated.
