C O M M U N I C A T I O N S
Table 1. Enantioselective Hydrogenation of 2a-ma
Supporting Information Available: Experimental procedures and
X-ray crystallographic data (CIF) for 2e-h and 4g. This material is
entry
2
1
3
ee (%)b
1c
2
3
2a
2b
2c
2d
2e
2f
2g
2h
2i
1a
1a
1a
1a
1a
1a
1a
1a
1a
1b
1b
1b
1b
3a
3b
3c
3d
3e
3f
3g
3h
3i
98 (-)
91 (-)
96 (-)
88 (+)
94 (-)
97 (-)
94 (-)
93 (-)
62 (-)
76 (-)
91 (+)
81 (-)
92 (-)
References
4
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5
6d
7e
8
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a P(H2) ) 3 MPa, 80 °C, imide:1:KOtBu ) 10:1:1, [imide] )
0.02-0.2 M in 2-propanol, >99% conversion. b HPLC analysis using a
Daicel Chiralcel or Chiralpak column. The sign of rotation is indicated
in parentheses. c Reference 6c. d 48 h. e The absolute configuration of 3g
was indicated to be 1R,3S on the basis of the absolute structure of 4g,
which was determined by X-ray diffraction study using the Flack
absolute structure parameters (see the Supporting Information).
Scheme 2. Stereospecific Transformations of 3g and an ORTEP
Diagram of 4g
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tathesis to give 2h exclusively. See the Supporting Information for details.
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unknown oligo- or poly(amides) with a rigid chiral cyclic skeleton
in the repeat unit as new members of the δ-peptide or 5-nylon
family,12 which are anticipated to form ordered secondary struc-
tures.13 Furthermore, reduction of 3g with LiAlH4 provided a chiral
δ-aminoalcohol (6g, Scheme 2), which should enjoy widespread
use as a platform for optically active ligands in catalytic asymmetric
synthesis.14 Therefore, our hydrogenative desymmetrization may
constitute a viable method in asymmetric synthesis.
In summary, we have found that suitably designed chiral Cp*Ru(PN)
catalyst systems promote hydrogenation of symmetrically structured
bicyclic imides to provide a variety of new chiral cyclic hydroxyamides
in a highly enantioselective manner. This work also unequivocally
demonstrates that modular design of chiral molecular catalysts can
provide direct access to stereochemically well-defined molecules, which
might otherwise have required a detour to reach.
Acknowledgment. This research was supported by the MEXT
(Nos. 16750073 and 18065007 “Chemistry of Concerto Catalysis”)
and by the Asahi Glass Foundation (M.I.).
(14) For example, see: Garc´ıa Mart´ınez, A.; Teso Vilar, E.; Garc´ıa Fraile, A.;
de la Moya Cerero, S.; Lora Maroto, B. Tetrahedron 2005, 61, 3055–3064.
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