C O M M U N I C A T I O N S
Scheme 3
catalysis. The diene ligand demonstrated its high and unique ability
in the rhodium-catalyzed asymmetric 1,4-addition of organoboron
and -tin reagents. We are now in a position to be able to design
new chiral diene ligands of higher ability and to apply them to a
variety of catalytic asymmetric reactions, especially to those where
the diene ligands are more suitable than other types of ligands in
catalytic activity.
Acknowledgment. This work was supported in part by a Grant-
in-Aid for Scientific Research from the Ministry of Education,
Science, Sports, and Culture, Japan.
Supporting Information Available: Experimental procedures,
spectroscopic and analytical data for the products (PDF). This material
References
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enantioface of the enones by the steric repulsions between the
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The diene (R,R)-1 demonstrates its remarkable ability as a chiral
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complexes. The rhodium-catalyzed 1,4-addition of organostannanes
is one of the typical examples.13 The reaction of phenyltrimethyl-
stannane (6m) with 2-cyclohexenone (2a) in the presence of 3 mol
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(Scheme 4). On hydrolysis, (R)-5am of 95% ee was obtained in
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J ) 7.2 Hz, 4H), 7.18 (tt, J ) 7.2, 1.2 Hz, 2H), 7.26 (t, J ) 7.2 Hz, 4H).
[R]20 +217 (c 1.02, CHCl3).
D
(8) [RhCl(R,R)-1)]2: 1H NMR (CDCl3): δ 0.76 (s, 4H), 3.07 (d, J ) 14.4
Hz, 4H), 3.50 (s, 4H), 3.75 (d, J ) 14.4 Hz, 4H), 3.79 (s, 4H), 7.17-7.47
(m, 20H).
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Scheme 4
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In summary, we have succeeded, for the first time, in the design
and preparation of a chiral diene as a chiral ligand for asymmetric
JA037367Z
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