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25444522675
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2] catalysts, see
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78650113199
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78751628370
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56
-
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79952821569
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-
note
-
Compounds 6 and 7 were obtained from the corresponding aldehyde (HCCMgBr (1.2 equiv), THF, RT (72 %; 6 / 7 =4:1). For determination of the configuration, 6 was transformed in three steps
-
-
-
-
57
-
-
79952858878
-
-
note
-
2, 0 °C to RT (93 %; 64:36)
-
-
-
-
58
-
-
79952839980
-
-
note
-
major diast.+PhSLi (0.95 equiv), -78 °C to RT (78 % conv.; 56 %)
-
-
-
-
59
-
-
79952820702
-
-
note
-
2SPh and the propargylic H.
-
-
-
-
60
-
-
79952844183
-
-
note
-
3 (1.2 equiv), LiCl (1.2 equiv), THF, RT (89 %).
-
-
-
-
62
-
-
79952830723
-
-
note
-
For the absolute configuration of 16, see Ref. [2b]. The absolute configuration of 17 was determined by correlation: 17 was oxidized, the resulting acid esterified and the ester side chain hydrogenated
-
-
-
-
63
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79952851448
-
-
note
-
2O, 45 °C, 2 h
-
-
-
-
64
-
-
79952859313
-
-
note
-
2 (1.2 equiv), toluene, 110 °C, 30 min, separation on chiral capillary column (CP-Chirasil-DEX CB (25 m à- 0.25 mm) (Chrompack)): second peak major
-
-
-
-
66
-
-
79952853132
-
-
note
-
2, RT, 97 %; 3) HCCMgBr (1.2 equiv), THF, RT (53 %+starting ketone (25 %)).
-
-
-
-
67
-
-
79952843943
-
-
note
-
4 under otherwise identical conditions gave only 14 % of rearranged product and 64 % of starting material.
-
-
-
-
68
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79952837192
-
-
note
-
Compounds 24 and 27 were prepared by addition of the corresponding methyl ketones to propargylmagnesium bromide (1.5 equiv) in THF in 91 and 47 % yield, respectively.
-
-
-
-
69
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-
79952853706
-
-
note
-
Migration of the cyclopropane C-C bond opposite to the C-Cï£M bond in M (Scheme 7) and P (Scheme 8) leads to the same metathesis product. These reactions proceed via non-classical cations, but for clarity we prefer not to draw partial bonds.
-
-
-
-
70
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0035814401
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For a related early study of platinum-catalyzed metathesis reactions leading to bridged bicyclic systems
-
For a related early study of platinum-catalyzed metathesis reactions leading to bridged bicyclic systems:, A. Fürstner, F. Stelzer, H. Szillat, J. Am. Chem. Soc. 2001, 123, 11863
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J. Am. Chem. Soc.
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Fürstner, A.1
Stelzer, F.2
Szillat, H.3
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71
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0032569211
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A. Fürstner, H. Szillat, B. Gabor, R. Mynott, J. Am. Chem. Soc. 1998, 120, 8305.
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J. Am. Chem. Soc.
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Fürstner, A.1
Szillat, H.2
Gabor, B.3
Mynott, R.4
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72
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79952840189
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Kindly performed by Professor M. Santelli (University of Aix-Marseille, France)
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Kindly performed by Professor M. Santelli (University of Aix-Marseille, France).
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