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For our detailed investigations into the mechanism of the O-directed alkylacetylene hydrostannation
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For our detailed investigations into the mechanism of the O-directed alkylacetylene hydrostannation, see: Dimopoulos, P.; George, J.; Manaviazar, S.; Tocher, D. A.; Hale, K. J. Org. Lett. 2005, 7, 5377-5380.
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For an account of our attempts to use this stannation method in the synthesis of the A83586C/kettapeptin pyran side-chain
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For an account of our attempts to use this stannation method in the synthesis of the A83586C/kettapeptin pyran side-chain, see: Hale, K. J.; Manaviazar, S.; George, J. Chem. Commun. 2010, 46, 4021-4042.
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For previous (+)-pumiliotoxin B total syntheses, see: (a) Overman, L. E.; Bell, K. L.; Ito, F. J. Am. Chem. Soc. 1984, 4192-4201;
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Eneyne asymmetric dihydroxylation: (a) Jeong, K.-S.; Sjo, P.; Sharpless, K. B. Tetrahedron Lett. 1992, 33, 3833-3836; For the AD procedure, see:
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For a related stereocontrolled iodohydroxylation on the N-benzoyl-pyrrolidine analogue of 11 This example proceeded with 10:1 stereoselectivity in favour of the desired tertiary alcohol-iodide, but unfortunately, difficulties were subsequently encountered in the removal of the N-benzoyl group. A priori, we considered that use of an N-trifluoroacetamide might overcome these difficulties and give rise to an identical stereochemical outcome, and lead to 10 with good stereocontrol
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For a related stereocontrolled iodohydroxylation on the N-benzoyl-pyrrolidine analogue of 11 see: Overman, L. E. McCready, R. J. Tetrahedron Lett. 1982, 23, 4887. This example proceeded with 10:1 stereoselectivity in favour of the desired tertiary alcohol-iodide, but unfortunately, difficulties were subsequently encountered in the removal of the N-benzoyl group. A priori, we considered that use of an N-trifluoroacetamide might overcome these difficulties and give rise to an identical stereochemical outcome, and lead to 10 with good stereocontrol.
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3N Swern-type oxidation, we now have good reason to suspect that the latter process may have epimerized the C(11)-centre before the alkynylation was effected. Our future full account will look into this step again
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3N Swern-type oxidation, we now have good reason to suspect that the latter process may have epimerized the C(11)-centre before the alkynylation was effected. Our future full account will look into this step again.
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