C O M M U N I C A T I O N S
combined with an achiral Brønsted base.17,20 The combination of
the achiral bulky 2,6-biarylpyridine (2) with the simple disulfonic
acid (1) circumvented the trouble of having to build bulky
substituents at the 3,3′-position as is normally required in the
analogous binaphthyl phosphoric acid catalysts. In the presence of
1 mol % of 1 and 2 mol % of 2, highly enantioselective direct
Mannich-type reactions of a variety of 1,3-diketones and a 1,3-
ketoester equivalent with arylaldimines proceeded smoothly with
high enantioselectivities. We believe that BINSA should be a
powerful chiral auxiliary like BINOL, BINAP (2,2′-bis(diphe-
nylphosphino)-1,1′-binaphthalene), BINAM (2,2′-diamino-1,1′-bi-
naphthalene), etc., and could trigger a new frontier in acid-base
chemistry in asymmetric catalyses.
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Acknowledgment. Financial support for this project was
provided by JSPS, KAKENHI (Grant 20245022), Grant-in-Aid for
Young Scientists B of MEXT (Grant 19750072), the G-COE
Program of MEXT, Toray Science Foundation, Iketani Science and
Technology Foundation, and Izumi Science and Technology
Foundation. T.M. acknowledges a JSPS Fellowship for Japanese
Junior Scientists. This paper is dedicated to Professor Elias J. Corey
on the occasion of his 80th birthday.
Supporting Information Available: Experimental procedures and
the comparisons with a chiral phosphoric acid catalyst. This material
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(b) Bandarage, U. K.; Simpson, J.; Smith, R. A. J.; Weavers, R. T.
Tetrahedron 1994, 50, 3463.
(12) Compound 5 is commercially available from International Laboratory,
Interchim, and WaterstoneTech.
References
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(17) To understand the character of our catalysts, we also examined some
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Supporting Information in detail.
(18) Probably, 1 · 2 rather than 1 · 22 may be the active species in situ, since
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Scheme 3, and eq 2. Also see ref 6j.
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16860 J. AM. CHEM. SOC. VOL. 130, NO. 50, 2008