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25. (a) Christophers , J. ; Baro , A. (Eds.). Quaternary Stereocenters: Challenges and Solutions for Organic
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(b)
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26. In one study, the anti-alkylidene isomer has been shown to be more reactive than the syn-isomer in
the ring - opening - metathesis polymerization of 2,3 - bis(trifl uoromethyl)norbornadiene. See: Oskam , J.
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27. Use of OsO 4 leads to low regioselectivity. For use of chiral dihydroxylation catalysts in synthesis, see:
(a) Kolb , H. C. ; VanNieuwenhze , M. S. ; Sharpless , K. B. Chem. Rev. 1994 , 94 , 2483 - 2547 . For catalytic
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28. For racemic syntheses of molecules, bearing a stereogenic axis, through metathesis, see: (a) Ahmed,
M. ; Arnauld , T. ; Barrett , A. G. M. ; Braddock , D. C. ; Flack , K. ; Procopiou , P. A. Org. Lett. 2000 , 2 ,
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K. ; Grandbois , A. ; Vachon , M. P. ; Cote , J. Angew. Chem. Int. Ed. 2006 , 45 , 2923 - 2926 . For an example
of diastereoselective control of planar stereogenicity through metathesis with an achiral catalyst, see:
(d) Layton , M. E. ; Morales , C. A. ; Shair , M. D. J. Am. Chem. Soc. 2002 , 124 , 773 - 775 .
29. (a) Ogasawara , M. ; Watanabe , S. ; Fan , L. ; Nakajima , K. ; Takahashi , T. Organometallics 2006 , 25 ,
5201 - 5203 . For a related study, see: (b) Grandbois , A. ; Collins , S. K. Chem. Eur. J. 2008 , 14 ,
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30. The selectivity factor (k rel ) is calculated by the equation reported by Kagan, which is a fi rst - order
equation based on relative rates of enantiomers proceeding to a single product, and does not account
for other processes that consume the starting material, such as homodimerization; see: Kagan, H. B.;
Fiaud , J. C. Top. Stereochem. 1988 , 18 , 249 - 330 .
31. The mechanistic model proposed by the authors (Reference xxix) is inconsistent with previous mecha-
nistic studies regarding enantioselective olefi n metathesis with this class of catalysts.
32. (a) Malcolmson , S. J. ; Meek , S. J. ; Sattely , E. S. ; Schrock , R. R. ; Hoveyda , A. H. Nature 2008 , 456 ,
933 - 937 . (b) Sattely , E. S. ; Mekk , S. J. ; Malcolmson , S. J. ; Schrock , R. R. ; Hoveyda , A. H. J. Am.
Chem. Soc. 2009 , 131 , 943 - 953 . For additional examples of enantioselective transformations with this
class of catalysts, see: (c) Ibrahem , I. ; Yu , M. ; Schrock , R. R. ; Hoveyda , A. H. J. Am. Chem. Soc. 2009 ,
131 , 3844 - 3845 . (d) Lee , Y. - J. ; Schrock , R. R. ; Hoveyda , A. H. J. Am. Chem. Soc. 2009 , 131 ,
10652 - 10661 .
33. (a) Solans - Monfort , X. ; Clot , E. ; Cop é ret , C. ; Eisenstein , O. J. Am. Chem. Soc. 2005 , 127 , 14015 - 14025 .
(b) Poater , A. ; Solans - Monfort , X. ; Clot , E. ; Cop é ret , C. ; Eisenstein , O. J. Am. Chem. Soc. 2007 , 129 ,
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34. (a) La , D. S. ; Ford , J. G. ; Sattely , E. S. ; Bonitatebus , P. J. ; Schrock , R. R. ; Hoveyda , A. H. J. Am.
Chem. Soc. 1999 , 121 , 11603 - 11604 . For a full account of this work, see: (b) La , D. S. ; Sattely , E. S. ;
Ford , J. G. ; Schrock , R. R. ; Hoveyda , A. H. J. Am. Chem. Soc. 2001 , 123 , 7767 - 7778 .
35. For previously reported enantioselective RORCM processes that do not involve norbornenes, see:
(a) Weatherhead , G. S. ; Ford , J. G. ; Alexanian , E. J. ; Schrock , R. R. ; Hoveyda , A. H. J. Am. Chem.
Soc. 2000 , 122 , 1828 - 1829 . (b) Cefalo , D. R. ; Kiely , A. F. ; Wucherer , M. ; Jamieson , J. Y. ; Schrock ,
R. R. ; Hoveyda , A. H. J. Am. Chem. Soc. 2001 , 123 , 3139 - 3140 . (c) Teng , X. ; Cefalo , D. R. ; Schrock ,
R. R. ; Hoveyda , A. H. J. Am. Chem. Soc. 2003 , 125 , 10779 - 10784 .
36. Weatherhead , G. S. ; Cortez , G. A. ; Schrock , R. R. ; Hoveyda , A. H. Proc. Natl. Acad. Sci. U.S.A. 2004 ,
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