DOI: 10.1016/s0040-4039(97)01433-0. Asymmetric Catalytic Alkylation of Aldehydes with Diethylzinc Using a Chiral Binaphthol-Titanium Complex

Asymmetric Catalytic Alkylation of Aldehydes with Diethylzinc Using a Chiral Binaphthol-Titanium Complex

10.1016/s0040-4039(97)01433-0

Crossref journal-article

Elsevier BV

Tetrahedron Letters (78)

Bibliography

Mori, M., & Nakai, T. (1997). Asymmetric Catalytic Alkylation of Aldehydes with Diethylzinc Using a Chiral Binaphthol-Titanium Complex. Tetrahedron Letters, 38(35), 6233â6236.

Authors 2

Maki Mori (first)
Takeshi Nakai (additional)

References 18 Referenced 155

Reviews: (a) Mikami, K.; Terada, M.; Narisawa, S.; Nakai, T. Synlett 1992, 255-265. (10.1055/s-1992-21333)
(a) Mikami, K.; Terada, M.; Narisawa, S.; Nakai, T. Synlett 1992, 255-265. (10.1055/s-1992-21333)
(b) Mikami, K.; Terada, M.; Narisawa, S.; Nakai, T. In Advances in Catalytic Processes; Doyle, M.P., Ed.; JAI Press, Inc: London, 1995; 1, p 123-149. (10.1016/S1874-5156(06)80008-9)
10.1016/0040-4039(95)00134-X / Tetrahedron Lett. by Kitamoto (1995)
10.1055/s-1996-5726 / Synlett by Imma (1996)
Mori, M.; Imma, H.; Nakai, T., the preceding paper.
For the asymmetric catalytic alkylations of aldehydes with organozinc reagents using chiral titanium catalysts in particular, see:(a) Seebach, D.; Beck, A.K.; Schmidt, B.; Wang, Y.M. Tetrahedron 1994, 50, 4363-4384. (10.1016/S0040-4020(01)89373-X)
Kobayashi, S. Tetrahedron 1992, 48, 5691-5700. (c) Soai, K. (10.1016/0040-4020(92)80020-G)
Niwa, S. Chem. Rev. 1992, 92. 833-856. (d) Soai, K. (10.1021/cr00013a004)
Hayase, T. J. Synth. Org. Chem., Jpn. 1995, 53, 138-150. (10.5059/yukigoseikyokaishi.53.138)
(a) Seebach, D.; Beck, A.K.; Schmidt, B.; Wang, Y.M. Tetrahedron 1994, 50, 4363-4384. (10.1016/S0040-4020(01)89373-X)
(b) Takahashi, H.; Kawakita, T.; Ohno, M.; Yoshioka, M.; Kobayashi, S. Tetrahedron 1992, 48, 5691-5700. (10.1016/0040-4020(92)80020-G)
(c) Soai, K.; Niwa, S. Chem. Rev. 1992, 92. 833-856. (10.1021/cr00013a004)
(d) Soai, K.; Hayase, T. J. Synth. Org. Chem., Jpn. 1995, 53, 138-150. (10.5059/yukigoseikyokaishi.53.138)
After this work was presented at the 70th Annual Meeting of the Chemical Society of Japan, March, 1996, Tokyo, Abstract 1J305, Chan and his co-workers have recently reported the addition reaction of diethylzinc to aromatic aldehydes catalyzed by essentially the same BINOL-Ti complex as reported herein: Zhang, F.-Y.; Yip, C.-W.; Cao, R.; Chan, A.S.C. Tetrahedron:Asymm. 1997, 8, 585–589. This publication prompted us to disclose our own results which include the reactions with aliphatic aldehydes and more detailed mechanistic aspects of this reaction. (10.1016/S0957-4166(97)00024-4)
The following procedure is representative. A solution of (S)-BINOL (0.2 mmol) and Ti(Oi-Pr)4 (1.2 mmol) in toluene (3 mL) was stirred at room temperature for 30 min. To the solution of Et2Zn (3 mL of 1.0 M solution in hexane; 3 mmol) was added at −78 °C. The resulting mixture was stirred for 30 min, and benzaldehyde (1 mmol) was added. The resulting mixture was gradually warmed to 0 °C and stirred for 1 h at that temperature. After hydrolysis with 2 mL of sat. NH4Cl soln., the mixture was allowed to slowly warm up to room temperature and was then filtered through Celite to remove the solid formed. Usual workup followed by silica gel column chromatography afforded the corresponding alcohol. The enantiomeric purity was determined by GC on chiral column.
A dimeric structure has been reported for the crystal structure of complex A: Martin, C. A. Ph. D. Thesis, MIT, 1988. Cf. Imma, H. Master Thesis, Tokyo Institute of Technology, 1995.
The dichiral complex E, if it acts as a precatalyst, should provide a different %ee from that of the monochiral complex F, thus the overall %ee depending, more or less, on %conversion.

Dates

Type	When
Created	23 years, 1 month ago (July 25, 2002, 9:33 a.m.)
Deposited	3 years, 2 months ago (June 24, 2022, 9:58 p.m.)
Indexed	4 days, 4 hours ago (Aug. 23, 2025, 12:58 a.m.)
Issued	27 years, 11 months ago (Sept. 1, 1997)
Published	27 years, 11 months ago (Sept. 1, 1997)
Published Print	27 years, 11 months ago (Sept. 1, 1997)

Funders 2

Japan Society for the Promotion of Science 10.13039/501100001691
Region: Asia
gov (National government)
Labels6
1. KAKENHI
2. 日本学術振興会
3. Gakushin
4. JSPS KAKEN
5. JSPS Grants-in-Aid for Scientific Research
6. JSPS
Ministry of Education, Culture, Sports, Science and Technology 10.13039/501100001700
Region: Asia
gov (National government)
Labels3
1. Monbu-kagaku-shō
2. 文部科学省
3. MEXT

BibTeX

@article{Mori_1997, title={Asymmetric Catalytic Alkylation of Aldehydes with Diethylzinc Using a Chiral Binaphthol-Titanium Complex}, volume={38}, ISSN={0040-4039}, url={http://dx.doi.org/10.1016/s0040-4039(97)01433-0}, DOI={10.1016/s0040-4039(97)01433-0}, number={35}, journal={Tetrahedron Letters}, publisher={Elsevier BV}, author={Mori, Maki and Nakai, Takeshi}, year={1997}, month=sep, pages={6233–6236} }

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