Intramolecular Pd-catalyzed carboetherification and carboamination. Influence of catalyst structure on reaction mechanism and product stereochemistry

Journal of the American Chemical Society

Volumn 128, Issue 9, 2006, Pages 2893-2901

  Nakhla, Josephine S ^a   Kampf, Jeff W ^a   Wolfe, John P ^a  

^a UNIVERSITY OF MICHIGAN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; AMINATION; BENZENE; CATALYSIS; CATALYSTS; OXYGEN; PALLADIUM; STEREOCHEMISTRY;

ARENE; CARBOAMINATION; CARBOETHERIFICATION;

OLEFINS;

ALKENE DERIVATIVE; BENZENE; INDAN DERIVATIVE; LIGAND; PALLADIUM COMPLEX; POLYCYCLIC AROMATIC HYDROCARBON; PYRROLIDINE DERIVATIVE; TETRAHYDROFURAN DERIVATIVE;

ADDITION REACTION; ARTICLE; CARBOAMINATION; CARBOETHERIFICATION; CATALYSIS; CATALYST; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; DIASTEREOISOMER; QUANTUM YIELD; REACTION ANALYSIS; STEREOCHEMISTRY;

ALKENES; AMINATION; BENZENE DERIVATIVES; CATALYSIS; CYCLIZATION; FURANS; NAPHTHALENES; ORGANOMETALLIC COMPOUNDS; PALLADIUM; PYRROLIDINES; STEREOISOMERISM;

EID: 33644950137     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja057489m     Document Type: Article

References (75)

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24. In our previous studies, we have noted that the large majority of products formed in intermolecular carboetherification and carboamination reactions of internal alkenes derive from syn-insertion of the alkene into the Pd-heteroatom bond of intermediate Pd(Ar)(OR) or Pd(Ar)(NRR′) complexes. See refs 7b and 7d.
25. (a) Through a series of deuterium labeling studies, Hayashi and co-workers have demonstrated that the Pd(II)-catalyzed oxidative cyclization of an o-allylphenol derivative proceeds via anti-alkoxypalladation in the presence of LiCl, and via syn-alkoxypalladation in the absence of LiCl. However, one of the stereocenters formed in these transformations is destroyed by the β-hydride elimination step that terminates the catalytic cycle. Thus, in the absence of labeled substrates, both transformations would provide identical products. See: Hayashi, T.; Yamasaki, K.; Mimura, M.; Uozumi. Y. J. Am. Chem. Soc. 2004, 126, 3036-3037.
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28. Previously described Wacker-type cyclizations of alkenes bearing tethered heteroatoms that afford tetrahydrofuran or pyrrolidine products generally proceed via a Pd(II)-Pd(0) catalytic cycle. The mechanism of these transformations involves complexation of the alkene to Pd(II) followed by nucleophilic attack of the tethered heteroatom and β-hydride elimination to generate the heterocyclic product. The resulting Pd(H)(X) complex undergoes reductive elimination of HX to provide a Pd(0) complex, which is then reoxidized to Pd(II) by an added oxidant. Catalysts employed for these reactions generally contain halide, carboxylate, or amine ligands rather than phosphine ligands. For further details, see: (a) Reference 13.
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31. (±)-BINAP = 2,2′-bis(diphenylphosphino)-1,1′- binaphthyl; DPP-benzene = 1,2-bis(diphenylphosphino)benzene.
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33. Further optimization experiments revealed that use of bases such as triethylamine and potassium carbonate did not afford the desired cyclization products.
34. Complete details on the synthesis of all substrates are provided in the Supporting Information.
35. Aldehyde products derived from oxidation of the primary alcohol moiety were not observed, but it is likely that these side products are not stable under the reaction conditions.
36. See the Supporting Information for complete details of stereochemical assignments.
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38. 3/BINAP catalyst system also provided the anti-addition product as the major diastereomer, albeit in low yield. Use of BINAP as ligand for the cyclization of 9 gave 35% yield (3:1 dr) of 7, and the cyclization of 11 proceeded to afford 24% yield (>20:1 dr) of 12 under similar conditions.
39. Only the major product diastereomer is shown in eqs 2-4, 6, and 7. The structures of the other minor diastereomers are shown in the Supporting Information.
40. The products were isolated in 40% yield as a 17:2:1:1 mixture of diastereomers. However, analysis of the crude reaction mixture indicated that the diastereomers were formed in a 9:2:1:1 ratio, suggesting that partial resolution of the diastereomers occurred upon Chromatographie purification.
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