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J.B. Johnson et al. / Tetrahedron 65 (2009) 3202–3210
at which time the THF was evaporated under reduced pressure.
Addition of 1 mL DMF over blowing Ar to the resulting residue
provided a solution (0.5 M) of the desired organozinc triflate.
in this work. Supplementary data associated with this article can be
4.7. General procedure for the rhodium/phosphoramidite-
catalyzed enantioselective desymmetrization of meso-cyclic
anhydrides
References and notes
1. Diederich, F.; Stang, P. J. Metal-Catalyzed Cross-Coupling Reactions; Wiley-VCH:
Weinheim, 1998.
2. For asymmetric cross-coupling reactions, see: (a) Hayashi, T. J. Organomet.
Chem. 2002, 653, 41 and references therein; See also (b) Arp, F. O.; Fu, G. C.
J. Am. Chem. Soc. 2005, 127, 10482; (c) Fischer, C.; Fu, G. C. J. Am. Chem.
Soc. 2005, 127, 4595.
The procedure will be illustrated with a specific example. An
oven-dried round bottom flask was charged with [Rh(COD)Cl]2
(6.0 mg, 0.012 mmol) and (ꢁ)-TADDOL-PNMe2 (13.1 mg,
0.024 mmol) in an inert atmosphere (N2) glove box. Upon removal
from the glove box, the flask was purged with Ar and 1.0 mL DMF
was added. The desired organozinc triflate (0.5 mmol), prepared
according to the above procedure, was added to the catalyst solu-
3. Use of acid chlorides: (a) Kosugi, M.; Shimizu, Y.; Migita, T. Chem. Lett. 1977,
1423; (b) Milstein, D.; Stille, J. K. J. Am. Chem. Soc. 1978, 100, 3636; (c) Milstein,
D.; Stille, J. K. J. Org. Chem. 1979, 44, 1613; Thioesters: (d) Tokuyama, H.; Yo-
koshima, S.; Yamashita, T.; Fukuyama, T. Tetrahedron Lett. 1998, 39, 3189; (e)
Liebeskind, L. S.; Srogl, J. J. Am. Chem. Soc. 2000, 122, 11260; (f) Wittenberg, R.;
Srogl, J.; Egi, M.; Liebeskind, L. S. Org. Lett. 2003, 5, 3033; Aryl trifluoroacetates:
(g) Kakin, R.; Shimizu, I.; Yamamoto, A. Bull. Chem. Soc. Jpn. 2001, 74, 371; Acyl
cyanides: (h) Duplais, C.; Bures, F.; Sapountzis, I.; Korn, T. J.; Cahiez, G.; Knochel,
P. Angew. Chem., Int. Ed. 2004, 43, 2968; Acid fluorides: (i) Zhang, Y.; Rovis, T.
J. Am. Chem. Soc. 2004, 126, 15964.
4. (a) Real, S. D.; Kronenthal, D. R.; Wu, H. Y. Tetrahedron Lett. 1993, 34, 8063; (b)
Goossen, L. J.; Ghosh, K. Angew. Chem., Int. Ed. 2001, 40, 3458; (c) Goossen, L. J.;
Ghosh, K. Eur. J. Org. Chem. 2002, 19, 3254; (d) Kakino, R.; Narahashi, H.; Shi-
mizu, I.; Yamamoto, R. Bull. Chem. Soc. Jpn. 2002, 75, 1333; (e) Kakino, R.; Ya-
sumi, S.; Shimizu, I.; Yamamoto, A. Bull. Chem. Soc. Jpn. 2002, 75, 137; (f)
Yamamoto, A. J. Organomet. Chem. 2002, 653, 5; (g) Frost, C. G.; Wadsworth, K. J.
Chem. Commun. 2001, 2316; (h) Wang, D.; Zhang, Z. Org. Lett. 2003, 5, 4645; (i)
Hong, Y.-T.; Barchuk, A.; Krische, M. H. Angew. Chem., Int. Ed. 2006, 45, 6885.
5. See Ref. 4. See also (a) Spivey, A. C.; Andrews, B. I. Angew. Chem., Int. Ed. 2001,
40, 3131; (b) Chen, Y.; McDaid, P.; Deng, L. Chem. Rev. 2003, 103, 2965; (c) Willis,
M. C. J. Chem. Soc., Perkins Trans. 1 1999, 1765; (d) Tian, S.-K.; Chen, Y.; Hang, J.;
Tang, L.; McDaid, P.; Deng, L. Acc. Chem. Res. 2004, 37, 621; (e) Bolm, C.; Ato-
diresei, I.; Schiffers, I.; Kanai, M.; Shibasaki, M. Org. Synth. 2005, 82, 120.
6. Shintani, R.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 1057.
7. (a) O’Brien, E. M.; Bercot, E. A.; Rovis, T. J. Am. Chem. Soc. 2003, 125, 10498; (b)
Bercot, E. A.; Rovis, T. J. Am. Chem. Soc. 2002, 124, 174; (c) Bercot, E. A.; Rovis, T.
J. Am. Chem. Soc. 2005, 127, 247; (d) Johnson, J. B.; Bercot, E. A.; Rowley, J. M.;
Coates, G. W.; Rovis, T. J. Am. Chem. Soc. 2007, 129, 2718; (e) Johnson, J. B.; Yu,
R. T.; Fink, P.; Bercot, E. A.; Rovis, T. Org. Lett. 2006, 8, 4307; (f) Rogers, R. L.;
Moore, J. M.; Rovis, T. Angew. Chem., Int. Ed. 2007, 46, 9301; (g) Johnson, J. B.;
Rovis, T. Acc. Chem. Res. 2008, 41, 327.
8. Bercot, E. A.; Rovis, T. J. Am. Chem. Soc. 2004, 126, 10248.
9. For a recent solution to this problem, see: Kim, J. G.; Walsh, P. J. Angew. Chem.,
Int. Ed. 2006, 45, 4175.
tion.
A solution of 2,3-dimethylsuccinic anhydride (38 mg,
0.3 mmol) in 1 mL DMF was added via syringe and the reaction
mixture was heated at 50 ꢀC in an oil bath. After 20 h, the reaction
mixture was diluted with 10 mL of Et2O and quenched with 10 mL
1 M aq HCl. The layers were separated and the aqueous layer
extracted with Et2O (2ꢂ10 mL). The combined organic layers were
extracted with 1 M aq Na2CO3 (2ꢂ5 mL), and the combined aque-
ous layers were brought to pH w1 with concentrated HCl. The
acidified aqueous layer was then extracted with Et2O (3ꢂ10 mL).
The combined organic layers were then washed with brine, dried
over MgSO4, filtered, and concentrated under reduced pressure to
yield desired ketoacid 7. For analysis of enantioselectivity, the
corresponding methyl ester was generated by treatment of the
ketoacid with TMSCHN2 (2.0 M in Et2O) in 3 mL of MeOH/PhH (1:1)
at 23 ꢀC for 5 min followed by quenching with AcOH.
Acknowledgements
Thanks to David Rubush for his invaluable assistance in pre-
paring this manuscript. J.B.J. thanks the National Institute of Health
for a postdoctoral fellowship. M.J.C. thanks the American Heart
Association for a postdoctoral fellowship. T.R. thanks Johnson and
Johnson, Merck, Eli, Lilly and Boehringer-Ingelheim for support. T.R.
is a fellow of the A.P. Sloan Foundation and thanks the Monfort
Family Foundation for a Monfort Professorship.
10. Hayashi, T.; Yamasaki, K. Chem. Rev. 2003, 103, 2829 and references therein.
11. Portion of this work have been communicated: See (a) Johnson, J. B.; Bercot, E.
A.; Williams, C. M.; Rovis, T. Angew. Chem., Int. Ed. 2007, 46, 4514; (b) Cook, M. J.;
Rovis, T. J. Am. Chem. Soc. 2007, 129, 9302.
12. The full results of this screen are provided in Supplementary data.
13. (a) Rozema, M. J.; AchyuthaRao, S.; Knochel, P. J. Org. Chem. 1992, 57, 1956; (b)
Langer, F.; Schwink, L.; Devasagayaraj, A.; Chavant, P.-Y.; Knochel, P. J. Org. Chem.
1996, 61, 8229; (c) Stadtmueller, H.; Knochel, P. Organometallics 1995, 14, 3163.
14. Fagnou, K.; Lautens, M. Angew. Chem., Int. Ed. 2002, 41, 26.
Supplementary data
Supplementary data includes general methods for the pro-
cedures described herein, and full results of the screens performed
15. Formation of the organozinc reagent was performed in THF. The solvent was
removed under vacuum and redissolved in DMF prior to use in reaction.