Desymmetrizing reductive aldol cyclizations of enethioate derivatives of 1,3-diones catalyzed by a chiral copper hydride
A range of enethioate derivatives of 1,3-diones underwent reductive aldol cyclizations catalyzed by a chiral copper hydride generated in situ from 5 mol% TaniaPhos (SL-T001-1), 5 mol% Cu(OAc)(2)·H(2)O, 5 mol% bipyridine and 2.0 equiv. of PhSiH(3), to furnish polycyclic β-hydroxythioester products be...
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| Veröffentlicht in: | Organic & biomolecular chemistry 2012-08, Vol.10 (30), p.5971-5978 |
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| container_title | Organic & biomolecular chemistry |
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| creator | Ou, Jun Wong, Wing-Tak Chiu, Pauline |
| description | A range of enethioate derivatives of 1,3-diones underwent reductive aldol cyclizations catalyzed by a chiral copper hydride generated in situ from 5 mol% TaniaPhos (SL-T001-1), 5 mol% Cu(OAc)(2)·H(2)O, 5 mol% bipyridine and 2.0 equiv. of PhSiH(3), to furnish polycyclic β-hydroxythioester products bearing three newly established contiguous stereocenters, with >98:2 dr and in up to 94% yield and 98% ee. The use of an amine such as bipyridine or 2,6-lutidine as additive results in an increase of the overall reaction rate. The major bicyclic aldol product has all substituents cis and can be rationalized by a reductively generated (Z)-enolate reacting with the dione via a cyclic transition state. |
| doi_str_mv | 10.1039/c2ob25206f |
| format | Article |
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The use of an amine such as bipyridine or 2,6-lutidine as additive results in an increase of the overall reaction rate. 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The use of an amine such as bipyridine or 2,6-lutidine as additive results in an increase of the overall reaction rate. 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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| title | Desymmetrizing reductive aldol cyclizations of enethioate derivatives of 1,3-diones catalyzed by a chiral copper hydride |
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