The Hydrovinylation Reaction:  A New Highly Selective Protocol Amenable to Asymmetric Catalysis

Hydrovinylation and Related Reactions: New Protocols and Control Elements in Search of Greater Synthetic Efficiency and Selectivity

“…Heterodimerization with other olefins: Unlike heterodimerization reactions of ethylene, a synthetically useful heterodimerization reaction that uses propene [7a,b, 17] was not developed until recently. We find [18] that propene reacts with styrene and substituted styrenes under conditions slightly modified from what was previously described for ethylene [11] and gives excellent yields of the expected products. An example of a substrate with a Lewis-basic acetoxy group is shown in Equation (3).…”

“…(4)]. [11] In addition, we also discovered that a minor modification in the ligand structure (12 b), with the use of ÀOCH 2 Ph instead of ÀOMe, improved the ee for MVN to 80 % when the reaction was carried out at À 70 8C. These weakly coordinating O-alkyl groups of the ligand appear to be crucial for the success of the reaction, since yield and enantioselectivity for the ligand with ethyl group (12 c) in place of the methoxy group are only 13 % and 3 % ee, respectively.…”

Übergangsmetallkatalysierte C‐C‐Kupplungen mit Ethylen im Labormaßstab

“…[31] Exzellente Ausbeuten und mittlere Enantioselektivitäten wurden mit den von Hayashi und Mitarbeitern [32] [37] verschiedenen Pyrrolidinoindolinen [38] und Pseudopterosinen. [39] 4 [40,43] Cobaltkatalysierte Hydrovinylierungen von verschiedenen 1,3-Dienen mit Alkenen sind schon seit einiger Zeit bekannt, [44] allerdings waren Vogt und Mitarbeiter die ersten, die eine enantioselektive Hydrovinylierung von Styrol durch chirale zweizähnige Phosphanliganden beschrieben.…”

Transition Metal Catalyzed Coupling Reactions under C−H Activation

“…[42g] C À C coupling reactions that are based on ªintermolecularº catalytic CÀH activation on otherwise nonactivated sp 2 -and especially sp 3 -hybridized centers continue to represent a challenge. Such coupling processes are rare.…”

“…The Heck reaction [2] and hydrovinylation [3] are not be considered in this review: in these processes CÀH activation occurs only after CÀC coupling. CÀH activations for CÀHeteroatom coupling, [4] among them oxidation reactions such as the one with Bartons Gif systems are also not discussed in this review.…”