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For a model study, see: D. Song, G. Blond, A. F rstner, Tetrahedron 2003, 59, 6899-6904.
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0001425899
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2 (93% inhibition at 4.4 mm concentration) whereas 4 is a feeding deterrent for herbivorous gastropods and sea urchins and therefore likely plays a role for the chemical defense of the producing algae, see
-
Compound 1 inhibits phospholipase A2 (93% inhibition at 4.4 mm concentration) whereas 4 is a feeding deterrent for herbivorous gastropods and sea urchins and therefore likely plays a role for the chemical defense of the producing algae, see: a) A. M. S. Mayer, V. J. Paul, W. Fenical, J. N. Norris, M. S. de Carvalho, R. S. Jacobs, Hydrobiologia 1993, 260 - 261, 521 -529;
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84924098079
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Only the bromination of 4-pyrones devoid of additional unsaturations is known, see
-
Only the bromination of 4-pyrones devoid of additional unsaturations is known, see:
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10
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62349125019
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0018358430
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Reviews: a) P. Sharma, K. J. Powell, J. Burnley, A. S. Awaad, J. E. Moses, Synthesis 2011, 2865-2892;
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15
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84924175336
-
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Only 2-methoxy-4-pyrones are reasonably common in nature; for illustrative total syntheses of such compounds, see the following and literature cited therein
-
Only 2-methoxy-4-pyrones are reasonably common in nature; for illustrative total syntheses of such compounds, see the following and literature cited therein:
-
-
-
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16
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4344710275
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b) A. K. Miller, D. H. Byun, C. M. Beaudry, D. Trauner, Proc. Natl. Acad. Sci. USA 2004, 101, 12019-12023;
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33845342908
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15044350629
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33846550683
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20
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84863709681
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W.Chalstrok;adaj, M. Corbet, A. F rstner, Angew. Chem. Int. Ed. 2012, 51, 6929 -6933;
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Chaladaj, W.1
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21
-
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84924178695
-
-
This reaction enabled the total synthesis of neurymenolide A; although this compound is a 2-pyrone with a cyclophane scaffold, it is arguably the closest relative of 1-6 currently known
-
This reaction enabled the total synthesis of neurymenolide A; although this compound is a 2-pyrone with a cyclophane scaffold, it is arguably the closest relative of 1-6 currently known.
-
-
-
-
22
-
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84920146956
-
-
Our 2-pyrone synthesis has already been used by others, see
-
Our 2-pyrone synthesis has already been used by others, see: a) Y. Chen, L. Wang, N. Sun, X. Xie, X. Zhou, H. Chen, Y. Li, Y. Liu, Chem. Eur. J. 2014, 20, 12015-12019;
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23
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84904502255
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b) J. S. Lee, J. Shin, H. J. Shin, H.-S. Lee, Y.-J. Lee, H.-S. Lee, H. Won, Eur. J. Org. Chem. 2014, 4472-4476.
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84924124419
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[12]
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more..
-
38
-
-
84924200347
-
-
The corresponding allylic iodide underwent quantitative isomerization to the E-configured substitution product under otherwise identical conditions
-
The corresponding allylic iodide underwent quantitative isomerization to the E-configured substitution product under otherwise identical conditions.
-
-
-
-
39
-
-
84924207730
-
-
Details will be reported in a future full paper
-
Details will be reported in a future full paper.
-
-
-
-
41
-
-
78149425384
-
-
Protodeauration likely has to outperform diauration of the reactive intermediates
-
Protodeauration likely has to outperform diauration of the reactive intermediates, see: a) G.Seidel, C. W.Lehmann, A. F rstner, Angew. Chem. Int. Ed. 2010, 49, 8466 -8470;
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Seidel, G.1
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84864606288
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a) J. Heppekausen, R. Stade, A. Kondoh, G. Seidel, R. Goddard, A. F rstner, Chem. Eur. J. 2012, 18, 10281-10299;
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Heppekausen, J.1
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F rstner, A.6
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43
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77955563276
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45
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84924209424
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For applications of RCAM to other natural products of polyacetate origin
-
For applications of RCAM to other natural products of polyacetate origin, see:
-
-
-
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46
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84900792132
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47
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0034614071
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A. F rstner, K. Grela, C. Mathes, C. W. Lehmann, J. Am. Chem. Soc. 2000, 122, 11799-11805.
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48
-
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85009713288
-
-
H = 4.14 ppm in ref. [2]; for details see the Supporting Information
-
H = 4.14 ppm in ref. [2]; for details see the Supporting Information.
-
-
-
-
49
-
-
84924144683
-
-
Because theαD of 1 has not been reported, the absolute configuration cannot be defined
-
D of 1 has not been reported, the absolute configuration cannot be defined.
-
-
-
-
50
-
-
84924143970
-
-
For the sake of brevity, the -OH group in 16 was inverted and the resulting alcohol 20-epi-16 advanced to anti-1; for details, see the Supporting Information
-
For the sake of brevity, the -OH group in 16 was inverted and the resulting alcohol 20-epi-16 advanced to anti-1; for details, see the Supporting Information.
-
-
-
-
52
-
-
84880797667
-
-
For other instructive cases from our group, see
-
For other instructive cases from our group, see:a) G. Valot, C. S. Regens, D. P. O'Malley, E. Godineau, H. Takikawa, A. F rstner, Angew. Chem. Int. Ed. 2013, 52, 9534 -9538;
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Valot, G.1
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80052432277
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S.Benson, M.-P.Collin, A.Arlt, B.Gabor, R.Goddard, A. F rstner, Angew. Chem. Int. Ed. 2011, 50, 8739 -8744;
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f) G. Valot, D. Mailhol, C. S. Regens, D. P. O'Malley, E. Godineau, H. Takikawa, P. Philipps, A. F rstner, Chem. Eur. J. 2015, 21, 2398-2408.
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|