C O M M U N I C A T I O N S
Recrystallization of the precipitate from CH2Cl2 and i-PrOH gives
(Rax,R)-3d with 80% de.
nation of the enantiomeric excess of amines. This work was partially
supported by a Grant-in-Aid for Scientific Research on Priority Area
(No. 16033224, ‘‘Reaction Control of Dynamic Complexes”) from
the Ministry of Education, Culture, Sports, Science and Technology
of Japan, and Nagase Science and Technology Foundation.
Reactions of diastereomerically pure esters 3 with a variety of
nucleophiles were explored. Butyllithium was found to react with
(Rax,S)-3d10 selectively at phosphorus to give enantiomerically pure
(S)-3-octanol ((S)-2d)11-13 in 87% yield (eq 3). A similar reaction
of (Rax,R)-3d9 provides (R)-3-octanol ((R)-2d).12,13
Supporting Information Available: Experimental procedures and
characterization of new compounds, including spectral data. This
References
(1) (a) Wenzel, T. J.; Wilcox, J. D. Chirality 2003, 15, 256-270. (b) Kasai,
Y.; Taji, H.; Fujita, T.; Yamamoto, Y.; Akagi, M.; Sugio, A.; Kuwahara,
S.; Watanabe, M.; Harada, N.; Ichikawa, A.; Schurig, V. Chirality 2004,
16, 569-585. (c) Kusumi, T.; Yabuuchi, T.; Takahashi, H.; Ooi, T. J.
Synth. Org. Chem. Jpn. 2005, 63, 1102-1114.
(2) For reviews, see: (a) Topics in Current Chemistry; Schulz, S., Ed.;
Springer: Berlin, 2004; Vol. 239. (b) Topics in Current Chemistry; Schulz,
S., Ed.; Springer: Berlin, 2005; Vol. 240.
In contrast, reactions of ester 3g with amines take place
selectively at the chiral carbon (eqs 4 and 5). For example,
benzylamine participates in a stereospecific substitution reaction
with 3g to produce the amine 4 with a high enantiomeric excess.14
In a similar manner, piperidine reacts with 3g to form enantio-
merically pure tertiary amine 5. The specific rotations of the
products 4 and 515 demonstrate that the substitution reactions of
3g with amines proceed with inversion of configuration at the chiral
carbon atom.
(3) Jacques, J.; Fouquey, C. Organic Syntheses; Wiley & Sons: New York,
1989; Vol. 67, pp 1-12.
(4) Syntheses of phosphoric acid esters bearing a 1,1′-binaphthyl-2,2′-diyl
group have been carried out by using dithallium salt of 1,1′-bi-2-naphthol,
P(O)Cl3, and secondary alcohols: (a) Kato, N. J. Am. Chem. Soc. 1990,
112, 254-257. (b) Kato, N.; Iguchi, M.; Kato, Y. Tetrahedron: Asymmetry
1991, 2, 763-766.
(5) Naidu, M. S. R.; Bull, E. O. J.; Nagaraju, C. Indian J. Chem. 1990, 29B,
691-693.
(6) For descriptions of the use of phosphorus-containing CDAs for the
evaluation of chiral alcohols, see: (a) Alexakis, A.; Mutti, S.; Normant,
J. F.; Mangeney, P. Tetrahedron: Asymmetry 1990, 1, 437-440. (b) Hulst,
R.; de Vries, N. K.; Feringa, B. L. Tetrahedron: Asymmetry 1994, 5,
699-708. (c) Bredikhin, A. A.; Bredikhina, Z. A.; Nigmatzyanov, F. F.
Russ. Chem. Bull. 1998, 47, 411-416. (d) Bredikhin, A. A.; Bredikhina,
Z. A.; Gaisina, L. M.; Strunskaya, E. I.; Azancheev, N. M. Russ. Chem.
Bull. 2000, 49, 310-313. (e) Alexakis, A.; Chauvin, A.-S. Tetrahedron:
Asymmetry 2000, 11, 4245-4248. (f) Reymond, S.; Brunel, J. M.; Buono,
G. Tetrahedron: Asymmetry 2000, 11, 1273-1278. (g) Weix, D. J.;
Dreher, S. D.; Katz, T. J. J. Am. Chem. Soc. 2000, 122, 10027-10032.
(h) Li, K. Y.; Zhou, Z. H.; Chan, A. S. C.; Tang, C. C. Heteroat. Chem.
2002, 13, 93-95. (i) Wang, D. Z.; Katz, T. J. J. Org. Chem. 2005, 70,
8497-8502.
(7) For a description of CDAs bearing PdSe bond for the evaluation of chiral
alcohols, see: House, K. L.; O’Connor, M. J.; Silks, L. A.; Dunlap, R.
B.; Odom, J. D. Chirality 1994, 6, 196-201.
(8) For descriptions of the use of selenium-containing CDAs for the evaluation
of chiral alcohols, see: (a) Wu, R.; Odom, J. D.; Dunlap, R. B.; Silks, L.
A. Tetrahedron: Asymmetry 1995, 6, 833-834. (b) Silks, L. A.; Wu, R.;
Dunlap, R. B.; Odom, J. D. Phosphorus, Sulfur Silicon Relat. Elem. 1998,
136-138, 209-214.
The observations described above show that enantiomerically
pure 1,1′-binaphthyl-2,2′-diyl phosphoroselenoyl chloride (1),
readily prepared from PCl3, elemental selenium, and 1,1′-bi-2-
naphthol, is a new, multifunctioning chiral molecular tool. This
chloride can be used to resolve simple secondary alcohols. In
addition, selective cleavage of either the phosphorus-oxygen and
oxygen-carbon bonds in the esters 3, formed by reaction of 1 with
simple alcohols, can be accomplished without loss of enantiomeric
purity. Importantly, these cleavage reactions provide access to a
variety of optically active alcohols and amines with high enantio-
meric purities. The results of continuing studies in this area that
focus on the preparation of biologically important optically active
compounds and optically active ligands will be reported in due
course.
(9) See Supporting Information for details of the separation of esters 3a, 3c,
3d, and 3g.
(10) The esters 3d with high diastereomeric excess were obtained by HPLC
purification of the esters obtained in Scheme 1.
(11) Since optically active 3-octanol is a known pheromone, its synthesis and
isolation in enantiomerically pure form are important: (a) Cho, B. T.;
Kim, D. J. Tetrahedron 2003, 59, 2457-2462. (b) Ichikawa, A.; Ono, H.
Tetrahedron: Asymmetry 2005, 16, 2559-2568.
(12) Specific rotation of enantiomerically pure (S)- and (R)-2d is reported to
be [R]37D ) +10 (c ) 0.14, CHCl3) and [R]37D ) -8 (c ) 0.16, CHCl3),
respectively.11b
(13) The 31P NMR spectra of esters 3d, formed by reactions of alcohols (S)-
and (R)-2d with 1, each contain only a single signal.
(14) Enantiomeric excess of amine 4 is determined by HPLC (chiralcel AD-
H).
(15) The absolute configurations of the amines 4 and 5 are assigned by
comparison of their specific rotations with those reported. (a) For 4:
Cannata, V.; Samori, B.; Tramontini, M. Tetrahedron 1971, 27, 5247-
5254. (b) For 5: Pyne, S. G.; Griffith, R.; Edwards, M. Tetrahedron Lett.
1988, 29, 2089-2092.
Acknowledgment. We thank Professors Y. Tsuji and M.
Tokunaga and Dr. Obora at Hokkaido University for the determi-
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