Cyclopropanation - Carbohydrates: Tools for Stereoselective Synthesis - page 311

D-gluco

Me Me

AIh (1.1 mol%)
CuOTf 0.5 C 6 H 6 (1 mol%)

O O

O O

+ +

R 2

CO 2 Et N N

N 2

R 2 R 2

CO 2 Et CO 2 Et

CH 2 Cl 2

O O

23 10 24 trans 24 cis

O O O O

ee trans ee cis

trans/cis

Ph OHC CHO Ph

a R 2 = hexyl
b R 2 = heptyl

a R 2 = hexyl
b R 2 = heptyl

78%
75%

73:27
73:27

90%ee
90%ee

95%ee
95%ee

3-O-formyl glucoBox
( 9h )

6 steps

N

heptyl CO 2 Et heptyl Ph

67% yield

O

24b trans

(+)-grenadamide

ent 25

Scheme 14.2 Asymmetric cyclopropanation of non-activated aliphatic alkenes ( 23a,b ) with
ethyl diazoacetate ( 11 ) in the presence of optimized carbohydrate bis(oxazoline) 3- O -formyl
gluco Box ( 9h ). Stereoselective synthesis of ( + )-grenadamide ( ent - 25 ).

References

1 For reviews see: (a) Pellissier, H. (2008)
Tetrahedron , 64 , 7041; (b) Lebel, H.,
Marcoux, J.-F., Molinaro, C., and
Charette, A.B. (2003) Chem. Rev. , 103 ,
977; (c) Doyle, M.P. and Forbes, D.C.
(1998) Chem. Rev. , 98 , 911;
(d) Doyle, M.P. and Protopopova, M.N.
(1998) Tetrahedron , 54 , 7919.
2 (a) Taylor, R.E., Engelhardt, F.C., and
Schmitt, M.J. (2003) Tetrahedron ,
59 , 5623; (b) Donaldson, W.A.
(2001) Tetrahedron , 57 , 8589;
(c) Wessjohann, L.A., Brandt, W.,
and Thiemann, T. (2003) Chem. Rev. ,
103 , 1625.
3 (a) Desimoni, G., Faita, G., and
Jørgensen, K.A. (2006) Chem. Rev. , 106 ,
3561; (b) McManus, H.A. and Guiry, P.J.
(2004) Chem. Rev. , 104 , 4151;
(c) Desimoni, G., Faita, G., and
Quadrelli, P. (2003) Chem. Rev. , 103 , 315;
(d) Ghosh, A.K., Mathivanan, P., and
Capiello, J. (1998) Tetrahedron:
Asymmetry , 9 , 1.
4 (a) Evans, D.A., Woerpel, K.A.,
Hinman, M.M., and Faul, M.M. (1991)
J. Am. Chem. Soc. , 113 , 726; (b)
Loewenthal, R.E., Abiko, A., and
Masamune, S. (1990) Tetrahedron Lett. ,
31 , 6005.

5 Loewenthal, R.E., Abiko, A., and
Masamune, S. (1990) Tetrahedron Lett. ,
31 , 6005.
6 Irmak, M., Groschner, A., and Boysen,
M.M.K. (2007) Chem. Commun. , 177.
7 (a) Minuth, T. and Boysen, M.M.K.
(2008) Synlett , 1483; (b) Minuth, T.,
Irmak, M., Groschner, A., Lehnert, T.,
and Boysen, M.M.K. (2009) Eur. J. Org.
Chem. , 997.
8 (a) Nashed, M.A., Slife, C.W., Kiso, M.,
and Anderson, L. (1980) Carbohydr. Res. ,
82 , 237; (b) Foces-Foces, C., Cano, F.H.,
Bernabe, M., Penades, S., and Martin-
Lomas, M. (1984) Carbohydr. Res. , 135 , 1.
9 Minuth, T. and Boysen, M.M.K. (2010)
Beilstein J. Org. Chem. , 6 (23), doi:
10.3762/bjoc.6.23
10 Irmak, M., Lehnert, T., and Boysen,
M.M.K. (2007) Tetrahedron Lett. , 48 , 7890.
11 Minuth, T. and Boysen, M.M.K. (2010)
Synthesis , 2799.
12 For successful examples see: (a) with
planar chiral ligands: Lo, M.M.-C. and
Fu, G.C. (1998) J. Am. Chem. Soc. , 120 ,
10270; (b) with boron-bridged
bis(oxazolines): Mazet, C., Köhler, V.,
and Pfaltz, A. (2005) Angew. Chem. Int.
Ed. , 44 , 4888.