Reversal of regioselectivity in Wacker-Type oxidation of simple terminal alkenes and its paired interacting orbitals (PIO) analysis

Bulletin of the Chemical Society of Japan

Volumn 78, Issue 8, 2005, Pages 1555-1557

  Ogura, Toshihiko ^a   Kamimura, Ryuichiro ^a   Shiga, Akinobu ^b   Hosokawa, Takahiro ^a  

^a KOCHI UNIVERSITY OF TECHNOLOGY   (Japan)

^b SUMITOMO CHEMICAL CO LTD   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDES; CHEMICAL BONDS; ELECTRON ENERGY LEVELS; HYDROCARBONS; PALLADIUM; STEREOCHEMISTRY;

OXYPALLADATION; PAIRED INTERACTING ORBITALS (PIO) ANALYSIS; REGIOSELECTIVITY; WACKER-TYPE OXIDATION;

OXIDATION;

1 DECENE; ALCOHOL; ALDEHYDE; ALKENE DERIVATIVE; UNCLASSIFIED DRUG;

ANALYTIC METHOD; ARTICLE; CHEMICAL BOND; CHEMICAL MODIFICATION; OXIDATION; PAIRED INTERACTING ORBITAL ANALYSIS; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 23844469131     PISSN: 00092673     EISSN: None     Source Type: Journal    
DOI: 10.1246/bcsj.78.1555     Document Type: Article

References (19)

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12. In the case of MeOH, ∼24% of 1-decene was isomerized to 2- and 3-decene (5:1) under the conditions described in the text, and a mixture of 3- and 4-decanone (∼1:1) was formed in ∼22% yield for 0.5 h. Similar trends were observed with EtOH. However, in the cases of i-PrOH and t-BuOH, virtually no isomerization of 1-decene occurred in 0.5 h.
13. T. Motoki and A. Shiga, J. Comput. Chem., 25, 106 (2003).
14. B represent the extended Hückel energies of C, A, and B noted above. The bond lengths and angles in alkoxy groups (OR) were taken from the usual values, such as C-C = 1.54 Å and H-C-H = 109.5°.
15. a) T. Hosokawa, T. Ohta, S. Kanayama, and S.-I. Murahashi, J. Org. Chem., 52, 1758 (1987).
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18. As the reaction proceeds, water or hydroperoxypalladium(II) formed in situ must attack the alkene to induce the ketonization (see Ref. 8b). In fact, the relative formation of decanal in t-BuOH decreased with reaction time; e.g., 1/2 = 29/71 in 12% yield for 1 h.
19. C) of 6 conformers thus formed were compared, it was found that 2 or 3 conformers among them were highly stable and that their stabilities were not much different. Thus, the ΣOP values for EtOH and i-PrOH listed were deduced by averaging the ΣOP values of these 2 or 3 conformers.