Asymmetric cyclopalladation of dimethylaminomethylferrocene

Roles of Bases in Transition-Metal Catalyzed Organic Reactions

“…例如在图 10 的反应中, 当没有碱加入时, 只能得到钯与 底物 7 的普通加合物 PdCl 2 (7) 2 , 而在加入 1 equiv.的碱 后, 则能顺利反应以 84%的收率得到钯杂五元环产物 8 [17] . [17,18] Figure 10 Effect of NaOAc on the cyclopalladation [17,18] 过渡金属催化的反应中也有类似的过程. Fagnou 等 [13] Figure 11 Direct arylation of perfluorobenzenes and several pathways for base assisted mechanism [13] 19 Figure 12 Palladium-catalyzed intramolecular arylation [21] Pd Br Figure 14 Palladium-catalyzed C-H activation of methyl groups [23] 另外, 在很多 C-H 活化的反应中, 加入 PivOH 能 促进反应的进行 [21,24,25] .…”

Optically active (2-aminomethylferrocenyl) phosphines with the phosphorus chiral center

“…2.08 (3) .80 (2) .82 (2) .84 (2) .46 (3) .48 (2) .49 (2) .38 (2) (2) 1.71(3) C(Is)--CI (3) 1.78(4) Angle c0/deg (2) 108 (2) C (5) (14) 121(27 CI( I)--C(Is)--Cl (2) 114(2) CI( I )--C(ls)--Cl (3) 110 (2) CI (2)--C(Is)--Cl(3) 11 I (13) lithium and the mixture was stirred for 40 min. A mixture of complex I (0.2214 g, 0.576 retool) (laid -592-6~ CH2CI2, ee 89%) and diphenylmethylphosphine (0.2 mL, 1.075 retool) in THF (4 mL) was added dropwise to the reaction mixture.…”

Asymmetric cyclopalladation of 6-ferrocenyl-2,2′-bipyridine and 2-ferrocenyl-1,10-phenanthroline

“…After evaporation of the solvent, compound 1 was obtained in a yield of 0.010 g (68%). 1 (Acetonitrile)[2 (2,2´ bipyridin 6 yl)ferrocen 1 yl] palla dium tetrafluoroborate (6). Silver tetrafluoroborate (0.0145 g, 0.074 mmol) was added to a solution of complex 3 (0.0358 g, 0.074 mmol) in acetonitrile (30 mL), and the reaction mixture was stirred for 4 h (until the starting compound 3 was consumed, TLC monitoring, MeOH : CHCl 3 , 1 : 10, as the eluent).…”

“…The precipitate that formed was filtered off, the filtrate was concen trated, the residue was washed with diethyl ether and dried, and compound 6 was obtained in a yield of 0.035 g (92%). 1 …”

“…[1][2][3][4] In this connection, it is of interest to perform this reaction with such substrates as 6 ferrocenyl 2,2´ bipyridine (1) and 2 ferrocenyl 1,10 phenanthro line (2). 5, 6 This may provide a route to optically active derivatives of these systems, which have found use in photophysics.…”