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The only available Pt-mediated oxycyclization of a γ-allenol is the 6-endo eyelization of 2,2-diphenyl-hexa-4,5-dien-1-ol leading lo 6-methyl-3,3-diphenyl-3,4-dihydro-2H-pyran. See: Z. Zhang, C. Liu, R. E. Kinder, X. Han, H. Qian, R. A. Widenhoefer, J. Am. Chem. Soc. 2006, 128, 9066.
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The only available Pt-mediated oxycyclization of a γ-allenol is the 6-endo eyelization of 2,2-diphenyl-hexa-4,5-dien-1-ol leading lo 6-methyl-3,3-diphenyl-3,4-dihydro-2H-pyran. See: Z. Zhang, C. Liu, R. E. Kinder, X. Han, H. Qian, R. A. Widenhoefer, J. Am. Chem. Soc. 2006, 128, 9066.
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The formation of all carbon quaternary centers in an asymmetric manner is one of the most difficult problems in organic chemistry, not leasl because the process requires the creation of a new C-C bond at a hindered center. For recent selected reviews, see: a P. G. Cozzi, R. Hilgraf, N. Zimmermann, Chem. 2007, 5969;
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The formation of all carbon quaternary centers in an asymmetric manner is one of the most difficult problems in organic chemistry, not leasl because the process requires the creation of a new C-C bond at a hindered center. For recent selected reviews, see: a) P. G. Cozzi, R. Hilgraf, N. Zimmermann, Eur. J. Org. Chem. 2007, 5969;
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As far as we known, the Pd-catalyzed cyclizative coupling reaction of γ-allenols with allyl halides has not yet been reported. For its pioneered used in α-allenols, see: S. Ma, W. Gao, J. Org. Chem. 2002, 67, 6104.
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To the best of our knowledge, no catalytic deprotection of MOM ethers has previously been reported. This unprecedented gold- and palladium-catalyzed MOM ether cleavage is extremely mild and selective. For comprehensive reviews, see: a, 4th ed, Wiley, New York
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To the best of our knowledge, no catalytic deprotection of MOM ethers has previously been reported. This unprecedented gold- and palladium-catalyzed MOM ether cleavage is extremely mild and selective. For comprehensive reviews, see: a) P. G. M. Wutz, T. W. Greene. Protective Groups in Organic Synthesis, 4th ed., Wiley, New York, 2006;
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The preferential regioselective 7-endo cyclization here differs markedly from that of the only reported La-mediated oxycyclization of a γ-allenol, namely the 6-endo/6-exo cyclization of hexa-4,5-dien-1-ol leading to 6-methyl-3,4-dihydro-2H-pyran and 2-methylenetetrahydro-2H-pyran as a 4:1 mixture. See reference [15].
-
The preferential regioselective 7-endo cyclization here differs markedly from that of the only reported La-mediated oxycyclization of a γ-allenol, namely the 6-endo/6-exo cyclization of hexa-4,5-dien-1-ol leading to 6-methyl-3,4-dihydro-2H-pyran and 2-methylenetetrahydro-2H-pyran as a 4:1 mixture. See reference [15].
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86
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60749083357
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Experimental procedures as well as full spectroscopic and analytical data for compounds not included in this Experimental Section are described in the Supporting Information. It contains as well copies of NMR spectra for all new compounds
-
Experimental procedures as well as full spectroscopic and analytical data for compounds not included in this Experimental Section are described in the Supporting Information. It contains as well copies of NMR spectra for all new compounds.
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