Ruthenium-catalyzed enyne cycloisomerizations. Effect of allylic silyl ether on regioselectivity

Journal of the American Chemical Society

Volumn 126, Issue 47, 2004, Pages 15592-15602

  Trost, Barry M ^a   Surivet, Jean Philippe ^a   Toste, F Dean ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL REACTIONS; COMPUTATIONAL GEOMETRY; HIGH TEMPERATURE EFFECTS; ISOMERIZATION; RUTHENIUM; SILANES;

DOUBLE BONDS; ENOL SILANES; SILANE GEOMETRY; TERMINAL ALLYLIC POSITION;

CATALYSIS;

ACETONE; ALKENE DERIVATIVE; ALKYNE DERIVATIVE; ALLYL COMPOUND; HETEROCYCLIC COMPOUND; RUTHENIUM; SILANE DERIVATIVE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; CHIRALITY; CYCLIZATION; GEOMETRY; ISOMERIZATION; ROOM TEMPERATURE; STEREOCHEMISTRY;

EID: 9644279363     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja046824o     Document Type: Article

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17. For Pd, see: Trost, B. M.; Tanoury, G. J.; Lautens, M.; Chan, C.; MacPherson, D. T. J. Am. Chem. Soc. 1994, 116, 4255-4267 and references therein. For Ni-Cr, see: Trost, B. M.; Tour, J. M. J. Am. Chem. Soc. 1987, 109, 5268-5270. For Ni, see: Radetich, B.; Rajan Babu, T. V. J. Am. Chem. Soc. 1998, 120, 8007-8008. For Co, see: Kraft, M. E.; Wilson, A. M.; Dasse, O. A.; Bonaga, L. V. R.; Cheung, Y. Y.; Fu, Z.; Shao, B.; Scott, J. L. Tetrahedron Lett. 1998, 38, 5911-5914. For Ti, see: Sturla, S. J.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 1976-1977. For Rh, see: Cao, P.; Wang, B.; Zhang, X. J. Am. Chem. Soc. 2000, 122, 6490-6491. For Ir, see: Chatani, N.; Inoue, H.; Morimoro, T.; Muto, T.; Murai, S. J. Org. Chem. 2001, 66, 4433-4436. See also: Trost, B. M.; Hashmi, A. S. K. Angew. Chem., Int. Ed. Engl. 1993, 32, 1085-1087. Chatani, N.; Kataoka, K.; Murai, S.; Furukawa, N.; Seki, Y. J. Am. Chem. Soc. 1998, 120, 9104-9105.
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54. After alkylation of ester 27 with the corresponding iodide, esters moitey were transformed in two steps (reduction to the alcohol and then Moffat-Swern oxidation) to the aldehydes, which were subjected to an excess of carbomethoxytriphenylphosphorane to yield respectively 28a or 28b. See Supporting Information section for more details.
55. These observations are consistent with the coupling constants we observed in the case of the intermolecular study; see ref 14.
56. The aldehyde was further reduced to the alcohol to ensure the standard characterizations.
57. The lower chemical yield is explained by a lower conversion.
58. The purity of 45 is crucial for the success of the isomerization, since we have noticed that contaminants (presumably hydrazine derivatives due to the Mitsunobu reaction) poisoned the catalyst.
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