The ortho-meta
lated comp
lex (
S,S)-[Pd
2{
2(
C,N)-C
6H
4CH
2CH(CO
2Me)NH
2-2}
2(
-Br)
2] (
1b) can beprepared by ref
luxing in acetonitri
le equimo
lecu
lar amounts of Pd(OAc)
2 and
L-pheny
la
lanine methy
lester hydroch
loride, fo
llowed by addition of an excess of NaBr. Comp
lex
1b reacts with 4-pico
line togive the mononuc
lear derivative (
S)-[Pd{
2(
C,N)
-C
6H
4CH
2CH(CO
2Me)NH
2-2}
2Br(NC
5H
4Me-4)] (
2),whose crysta
l structure has been determined by X-ray diffraction. The precursor of
1b, (
S,S)-[Pd
2{
2(
C,N)-C
6H
4CH
2CH(CO
2Me)NH
2-2}
2(
-C
l)
2] (
1a), cou
ld not be iso
lated in a pure form, but it can beused as the starting materia
l for the synthesis of functiona
lized derivatives of the pheny
la
lanine methy
lester. Thus, CO and RNC (R = Xy,
tBu) insert into the Pd-C bond of
1a to afford, after depa
lladation,(
S)-1-oxo-3-(methoxycarbony
l)-1,2,3,4-tetrahydroisoquino
line (
3) and (
S)-1-R-3-(methoxycarbony
l)-3,4-dihydroisoquino
linium trif
late (R =
tBu (
4), Xy (
5)), respective
ly. Reaction of comp
lex
1b with bromineor iodine affords
trans-(
S,S)-[PdBr
2{NH
2CH(CO
2Me)CH
2C
6H
4-X-2}
2] (X = Br (
6), I (
7)), which furtherreacts with 1,10-phenanthro
line (phen) to give [PdBr
2(phen)] and (
S)-2-X-pheny
la
lanine methy
l ester (X= Br (
8), I (
9)).