Lanthanide-Catalyzed Hydroamination of Hindered Alkenes in Synthesis:  Rapid Access to 10,11-Dihydro-5H-dibenzo- [a,d]cyclohepten-5,10-imines

Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium

“…The inclusion of alkyl groups on the terminal position of the alkene can be expected to disfavour the hydroamination reaction owing to the need to form an insertion transition state with partial tertiary Group II alkyl character. Similar observations have been made in organolanthanide chemistry, and a number of coordinatively unsaturated ansa-bridged metallocene and half-sandwich organolanthanide catalysts have been designed to effect the hydroamination/cyclization of highly substituted aminoalkenes (Molander & Dowdy 1999). Consistent with Baldwin's (1976) guidelines for ring formation, the ease of the catalytic reactions increases with decreasing ring size (5 > 6 > 7-membered ring closures).…”

Asymmetric Hydroamination

“…Internal 1,1-or 1,2-disubstituted olefins 26 and 28 are much less reactive for hydroamination and require significantly harsher reaction conditions [39,[41][42][43][44]. The formation of pyrrolidines and piperidines often proceeds at comparable rates (Eq.…”

Experimental and computational study on the energetics of 10,11-dihydro-5H-dibenzo[a,d]cycloheptene (dibenzosuberane)

“…These compounds have been reported as being antidepressants [2], the most well known being amitriptyline (3-(10,11-dihydro-5H-dibenzo[[a,d]]cycloheptene-5-ylidene)-N,N-dimethyl-1-propanamine) [3]. Dizocilpine (5-methyl-10, 11-dihydro-5H-dibenzo[a,d]cycloheptene-5,10-imine), also known as MK-801, displays potent anticonvulsant and neuroprotective properties [4][5][6][7].…”