Aminopalladation stereoselective

Furthermore, treatment of the aminopalladation product with bromine affords aziridines[176]. The aziridine 160 was obtained stereoselectively from methylamine and 1-decene in 43% yield. The aminopalladation of PdCl2 complexes of ethylene, propylene, and 1-butene with diethylamine affords the unstable ir-alkylpalladium complex 161, which is converted into the stable chelated acylpalladium complex 162 by treatment with CO[177],... 

Cyclization of 8-allenylamines is successful also. Synthesis of 2-alkenylpiperidines can be effected with mercury(II) or silver salts, with silver salts giving higher yields (equation 141 and Table 35).268a The significant asymmetric induction found in the cyclization of a chiral allene (78% ee, entry 2) suggests that the low stereoselectivity observed in the synthesis of the 2,6-disubstituted system (entry 3)269 may be a result of starting with a diastereomeric mixture. Aminopalladation/methoxycarbonylation has been effected in moderate yield also (entry 4). 

Backvall and coworkers have developed a stereoselective palladium catalyzed 1,4-addition to cyclic 1,3-dienes that produces pyrrolidine [89a] or lactam products [89bj. For example, treatment of 123 with catalytic Pd(OAc)2 and excess LiCl affords 125 (Eq. (1.50)). Alternatively, treatment of 123 with catalytic Pd(OAc)2 and excess LiOAc affords 127 (Eq. (1.51)). Both reactions proceed via awti-aminopalladation to afford an allylpalladium complex (124 or 126), which is then captured by an external nucleophile. Outer-sphere attack of chloride ion on 124 results in net syn-addition to the diene to give 125, whereas inner-sphere attack of acetate results in anti-addition to provide 127. 

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