Page 728 - Advanced Organic Chemistry Part B - Reactions & Synthesis

704 Scheme 8.7. Catalytic Enantioselective Conjugate Addition to Cyclohexenone

CHAPTER 8 Entry Reactant Catalyst Ligand Yield e.e.
Reactions Involving a n -C H MgCl
Transition Metals 1 4 9 CuI Ph 97 83
N
10 mol %
O
PPh
Fe 2
12 mol %
Ph P
2
3
2
2 5
2 b C H MgBr CuCl (H C) N 69 96
3 mol %
Fe PPh 2
6 mol %

3 2
3
2 5 2
3 c (C H ) Zn Cu(O SCF ) 94 >98
Ph
2 mol % O CH 3
P N
O CH 3
4 mol % Ph
4 d (C H ) Zn Cu(O SCF ) CH 3 96 90
3 2
2 5 2
3
2 mol % O
P O O
O
N
2.4 mol %
3 2
CH 3 C(CH )
5 e (C H ) Zn Cu(O SCF ) Ph Ph 90 71
3
3 2
2 5 2
CH 3 O O
1.2 mol %
P N(CH )
3 2
CH 3 O O
2.4 mol %
Ph Ph
6 f n -C 4 H 9 MgCl CuI 92 90
8 mol % N CH PPh 2
2
32 mol %
(CH ) N O
3 2
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b. B. L. Feringa, R. Badorrey, D. Pena, S. R. Harutyunyan, and A. J. Minnaard, Proc. Natl. Acad. Sci. USA,
101, 5834 (2004).
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36, 2620 (1997).
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56, 2879 (2000).
e. E. Keller, J. Maurer, R. Naasz, T. Schader, A Meetsma, and B. L. Feringa, Tetrahedron: Asymmetry, 9,
2409 (1998).
f. M. Kanai, Y. Nakagawa, and K. Tomioka, Tetrahedron, 55, 3843 (1999).