Insertion reactions of allenes with palladium aryl complexes [PdI(Ph)(PPh3)]2 and PdI(Ph)(dppe)

被引:37
作者
Bai, Tao [1 ]
Xue, Liqin [2 ]
Xue, Peng [2 ]
Zhu, Jun [2 ]
Sung, Herman Ho-Yung [2 ]
Ma, Shengming [1 ]
Wiliams, Ian Duncan [2 ]
Lin, Zhenyang [2 ]
Jia, Guochen [2 ]
机构
[1] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organomet Chem, Shanghai 200032, Peoples R China
[2] Hong Kong Univ Sci & Technol, Dept Chem, Hong Kong, Hong Kong, Peoples R China
关键词
D O I
10.1021/om800030a
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Treatment of [PdI(Ph)(PPh3)](2) with allenes CH2=C=CHR (R = CMe3, CO2Et, P(O)(OEt)(2), and SO2Ph) in dichloromethane at room temperature produces a mixture of cis and trans isomers of the a-allyl palladium complexes PdI(eta(3)-CH2C(Ph)CHR)(PPh3) in which the R group is anti to the Ph group. The disubstituted allenes MeCH=C=CHR (R = P(O)(OEt)(2) and SO2Ph) similarly react with [PdI(Ph)(PPh3)](2) to give the pi-allyl palladium complexes PdI(eta(3)-MeCHC(Ph)CHR)(PPh3) in which the R group is anti and the Me group is syn to the Ph group. PdI(Ph)(dppe) alone was found to be unreactive toward allenes such as CH2=C=CHSO2Ph and MeCH=C=CHSO2Ph at room temperature. In contrast, in the presence of TIPF6, PdI(Ph)(dppe) readily reacts with allenes CH2=C=CHR (R = CMe3, CO2Et, COPh, and SO2Ph) and MeCH=C=CHSO2Ph to give the pi-allyl palladium complexes [Pd(eta(3)-CH2C(Ph)CHR)(dppe)]PF6 and [Pd(eta(3)-MeCHC(Ph)CHR)(dppe)]PF6, respectively. Although mechanistically possible, vinyl complexes were not observed as the insertion products in all cases. The substituents of allenes appear to have no effect on the reaction pathways, at least for the allenes used in this study. The insertion reactions involving PdI(Ph)(PR3)(allene) have been studied by computational chemistry using the model complex PdI(Ph)(MeCH=C=CHSO2H)(PH3).
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页码:2614 / 2626
页数:13
相关论文
共 137 条
[41]   Palladium-catalyzed asymmetric reduction of allylic esters with a new chiral monodentate ligand, 8-diphenylphosphino-8′-methoxy-1,1′-binaphthyl [J].
Fuji, K ;
Sakurai, M ;
Kinoshita, T ;
Kawabata, T .
TETRAHEDRON LETTERS, 1998, 39 (35) :6323-6326
[42]   THE PATH OF CHEMICAL-REACTIONS - THE IRC APPROACH [J].
FUKUI, K .
ACCOUNTS OF CHEMICAL RESEARCH, 1981, 14 (12) :363-368
[43]  
GIGG R, 2006, SYNLETT, P3021
[44]  
Glendening E.D., NBO VERSION 3 1, Patent No. [NBO3.1, 31]
[45]   Golden times for allenes:: Gold-catalyzed cycloisomerization of β-hydroxyallenes to dihydropyrans [J].
Gockel, Birgit ;
Krause, Norbert .
ORGANIC LETTERS, 2006, 8 (20) :4485-4488
[46]   Allylpalladium complexes with P-stereogenic monodentate phosphines.: Application in the asymmetric hydrovinylation of styrene [J].
Grabulosa, A ;
Muller, G ;
Ordinas, JI ;
Mezzetti, A ;
Maestro, MA ;
Font-Bardia, M ;
Solans, X .
ORGANOMETALLICS, 2005, 24 (21) :4961-4973
[47]   Intermolecular Heck-Diels-Alder cascade processes of alkylallenes [J].
Grigg, R ;
Brown, S ;
Sridharan, V ;
Uttley, MD .
TETRAHEDRON LETTERS, 1998, 39 (20) :3247-3250
[48]   Stepwise successive insertion of carbon monoxide and allenes into palladium-carbon bonds of complexes containing the rigid bidentate nitrogen ligand bis(p-anisylimino)acenaphthene [J].
Groen, JH ;
Elsevier, CJ ;
Vrieze, K ;
Smeets, WJJ ;
Spek, AL .
ORGANOMETALLICS, 1996, 15 (15) :3445-3455
[49]   Kinetic study of the insertion of norbornadiene into palladium-carbon bonds of complexes containing the rigid bidentate nitrogen ligand bis(arylimino)acenaphthene [J].
Groen, JH ;
Delis, JGP ;
vanLeeuwen, PWNM ;
Vrieze, K .
ORGANOMETALLICS, 1997, 16 (01) :68-77
[50]   ALKALI-INDUCED DISPROPORTIONATION OF PALLADIUM(II) TERTIARY PHOSPHINE COMPLEXES, [L2PDCL2], TO LO AND PALLADIUM(0) - KEY INTERMEDIATES IN THE BIPHASIC CARBONYLATION OF ARX CATALYZED BY [L2PDCL2] [J].
GRUSHIN, VV ;
ALPER, H .
ORGANOMETALLICS, 1993, 12 (05) :1890-1901