Hydrostannation of norbornadiene by nBu3SnH and Ph3SnH with molybdenum catalysts

Tin(II) Hydrides as Intermediates in Rearrangements of Tin(II) Alkyl Derivatives

“…The exo regioselectivity of hydroboration of norbornene was also demonstrated, and calculations by Koga and co-workers showed that exo selectivity is preferred because of the lower energy required to deform the exo configuration relative to that of an endo form during the reaction . Sn­(IV) species were reported to hydrostannylate norbornadiene (NBD) to afford R 3 Sn­(norbornenyl) (R = n Bu, Ph) with transition-metal catalysts …”

“…25 Sn(IV) species were reported to hydrostannylate norbornadiene (NBD) to afford R 3 Sn(norbornenyl) (R = n Bu, Ph) with transition-metal catalysts. 26 It has been shown that the nortricylane isomers of NBD are more thermodynamically stable than the unsaturated bicyclic NBD form. 27 An anionic/free-radical pathway has been suggested for the rearrangement of a norbornenyl tin(IV) species to give tricyclo[2.2.1.0 2,6 ]heptane via a tin(IV) species (Scheme 1, path I).…”

Carbonyl Complexes of Molybdenum and their Catalytic Activity

“…Recently, it has been discovered that in addition to palladium catalysts, which are applied very frequently in this reaction, molybdenum carbonyl complexes can also be used as catalysts for the hydrostannation reaction [83][84][85][86][87][88]. In the presence of the molybdenum complex [MoBr( 3 -C 3 H 5 )(CO) 2 (NCMe) 2 ], tributyltin hydride adds instantaneously to various alkynes to give the corresponding vinylstannanes in good yields under mild conditions.…”

“…1:1 mixture of endo and exo isomers. The reaction was carried out at room temperature in n-heptane with continued photolysis at Mo(CO) 6 : R 3 SnH:nbd = 1:50:50 (Scheme 18) [88]. …”

“…Recent investigations of molybdenum carbonyl complexes have revealed novel types of their reactivity toward unsaturated organic compounds, e.g. in hydrosilylation hydrogermylation and hydrostannation of norbornadiene [78,80,88].…”