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To the best of our knowledge, there are no literature reports on the use of phosphine-phosphinites in allylic substitutions. However, phosphine-phosphites have been described: S. Deerenberg, H.S. Schrekker, G.P.F. van Strijdonck, P.C.J. Kamer, P.W.N.M. van Leeuwen, J. Fraanje, and K. Goubitz J. Org. Chem. 65 2000 4810 4817
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O. Pmies, G.P.F. van Strijdonck, M. Diéguez, S. Deerenberg, G. Net, A. Ruiz, C. Claver, P.C.J. Kamer, and P.W.N.M. van Leeuwen J. Org. Chem. 66 2001 8867 8871
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24
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11144356516
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For the use of supramolecular P-OP ligands in these transformations, see: V.F. Slagt, M. Roeder, P.C.J. Kamer, P.W.N.M. Van Leeuwen, and J.N.H. Reek J. Am. Chem. Soc. 126 2004 4056 4057
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77957150052
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4 for details on our synthetic strategy towards P-OP ligands 1-5
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4 for details on our synthetic strategy towards P-OP ligands 1-5.
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27
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33748941575
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77957157279
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note
-
In conditions identical to those of entry 2 in Table 2, 3-methyl-1-phenylbut-2-en-1-yl acetate was converted to (E)-dimethyl 2-(2-methyl-4-phenylbut-3-en-2-yl)malonate; and cyclohex-2-en-1-yl acetate gave the racemic substitution product.
-
-
-
-
33
-
-
77957113677
-
-
note
-
-, PF 6 - and BAr F -, respectively, indicating a tenuous counteranion effect.
-
-
-
-
34
-
-
77957121545
-
-
note
-
3-PhCHCHCHPh)(5)]Cl revealed that only two diastereoisomers were present in solution. Heavy signal overlapping did not allow us to unequivocally establish the structure of the two complexes 14 present in solution.
-
-
-
-
35
-
-
77957173833
-
-
note
-
Energetic and geometrical analysis at the full DFT-level of the transition structures for all possible reaction pathways is, even today, extremely time-consuming in systems of such complexity. Calculations on the geometries of the intermediate π-allyl complexes are much quicker and has allowed rationalisation of the stereochemical outcome of asymmetric allylic substitutions
-
-
-
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36
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0035914628
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(see for example: (a) Kollmar, M.; Goldfuss, B.; Reggelin, M.; Rominger, F.; Helmchen, G. Chem. Eur. J. 2001, 7, 4913-4927;
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38
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77957170774
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note
-
See Experimental for details on the geometry optimisation of complexes 14 at the DFT level. We did not consider the diastereoisomers 14-exo-anti-anti and 14-endo-anti-anti in the calculations, as nucleophilic attack on these substrates by DMM or BZA would lead to (Z)-alkenes 7a or 7d, respectively, neither of which we observed.
-
-
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39
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