K asymmetric reduction

Matsuo K, Kawabe S, Tokuda Y, Eguchi T, Yamanaka R, Nakamura K. Asymmetric reduction of ketones with a germinated plant. Tetrahedron Asymmetry 2008 19 157-159. 

Takemura T, Akiyama K, Umeno N, Tamai Y, Ohta H, Nakamura K. Asymmetric reduction of a ketone by knockout mutants of a cyanobacterium. J. Mol. Catal. B Enzym. 2009 60 93-95. 

Matsuda T, Marukado R, Mukouyama M, Harada T, Nakamura K. Asymmetric reduction of ketones by Geotrichum candidum immobilization and application to reaction using supercritical carbon dioxide. Tetrahedron Asymm. 2008 19 2272-2275. 

Nakamura, K., Yamanaka, R., Matsuda, T. and Harada, T. (2003) Recent developments in asymmetric reduction of ketones with biocatalysts. Tetrahedron Asymmetry, 14 (18), 2659—2681. 

Hummel, W., Abokitse, K., Drauz, K. et al. (2003) Towards a large-scale asymmetric reduction process with isolated enzymes Expression of an (5)-alcohol dehydrogenase in E. coli and studies on the synthetic potential of this biocatalyst. Advanced Synthesis and Catalysis, 345 (1 + 2), 153-159. 

Musa, M.M., Ziegelmann-Fjeld, K.I., Vieille, C. et al. (2007) Asymmetric reduction and oxidation of aromatic ketones and alcohols using W110A secondary alcohol dehydrogenase from Thermoanaerobacter ethanolicus. The Journal of Organic Chemistry, 72 (1), 30-34. 

Musa, M., Ziegelman-Fjeld, K., Vieille, C., Zeikus, J. and Phillips, R., Xerogel-encapsulated WHOA secondary alcohol dehydrogenase from Thermoanaerobacter ethanolicus performs asymmetric reduction of hydrophobic ketones in organic solvents. Angew. Chem. Int. Ed., 2007, 46, 3091-3094. 

Kometani et al. [71] reported that baker s yeast catalyzed the asymmetric reduction of acetol to (i )-1,2-propanediol with ethanol as the energy source. The enzyme involved in the reaction was an NADH-dependent reductase, and NADH required for the reduction was supplied by ethanol oxidizing enzyme(s) in the yeast. When washed cells of baker s yeast were incubated with 10 mg ml of acetol in an ethanol solution with aeration, (k)-1,2-propanediol was formed almost stoichiometrically with an optical purity of 98.2% e. e. 

Candida parapsilosis was found to be able to convert (k)-1,2-butanediol to (S)-l,2-butanediol through stereospecific oxidation and asymmetric reduction reactions [72]. The oxidation of (k)-1,2-butanediol to l-hydroxy-2-butanone and the reduction of l-hydroxy-2-butanone to (S)-l,2-butanediol were cataly-... 

T. Matsuda, T. Harada, N. Nakajima, and K. Nakamura, Mechanism for improving stereoselectivity for asymmetric reduction using acetone powder of microorganism, Tetrahedron Lett. 2000, 41, 4135 4138. 

Shimoda K, Kubota N et al (2004) Asymmetric reduction of a,P-unsaturated carbonyl compounds with reductases from Nicotiana tabacum. Tetrahedron Asymmetry 15 2443-2446... 

K Ishihara, N Nakajima, S Tsuboi, M Utaka. Asymmetric reduction of l-acetoxy-2-alkanones with bakers yeast purification and characterization of a-acetoxy ketone reductase. Bull Chem Soc Jpn 67 3314-3319, 1994. 

Yang JW, Hechavarria Fonseca MT, List B (2005) Catalytic asymmetric reductive Michael cyclization. J Am Chem Soc 127 15036-15037 Yoshikawa N, Chiba N, Mikawa T, Ueno S, Harimaya K, Iwata M (1994) Mitsubishi Chemical Industries patent. Jpn Kokai Tokkyo Koho JP 0630600 Zeitler K (2005) Extending mechanistic routes in heterazolium catalysis— promising concepts for versatile synthetic methods. Angew Chem Int Ed Engl 44 7506-7510... 

T. Nagata, K. Yorozu, T. Yamada, T. Mukaiyama, Angew. Chem. 1995, 107, 2309-2311 Angew. Chem. Int. Ed. Engl. 1995, 34, 2145-2147. For a recent review on the asymmetric reduction of carbonyl groups with hydrides,. see J. Seyden-Penne, Reductions by the Alumina- and Boro-hydrides in Organic Synthesis, 2nd edn., Wiley, New York, 1997, 55-84. 

The enantioselective synthesis of optically active secondary amines via asymmetric reduction of prochiral ketimines was studied by screening various chiral hydrides. In this case, K-glucoride gave only disappointing results and was inferior to other reagents. Better results were obtained in the asymmetric reduction of prochiral Af-diphenylphosphinylimines to chiral N-(diphenylphosphinyl)amines (eq 1), which can then be readily converted into optically active primary amines. For this reaction the stereochemical course depends dramatically on the relative bulkiness of the groups R and R. The reaction conditions for reduction of C=N double bonds are the same as used for ketones, but the high reactivity of diphenylphosphinylimines dramatically reduces the reaction time. 

Asymmetric reduction of prochiral diphenylphosphinylimines (111) by (S)-BINAL-H (28), LAH-Dar-von alcohol complex (48) or K-glucoride (64) affords the (S)-amines (112 Scheme 20). The protecting group of (112) is readily cleaved under acidic conditions to give the free amine. When the alkyl group is methyl or ethyl, (S)-BINAL-H shows high enantioselectivity. - ... 

Matsuda T, Watanabe K, Harada T, and Nakamura K. Enzymatic reactions in supercritical CO2 Carboxylation, asymmetric reduction and esterification. Catal. Today 2004 96(3) 103-111. 

E. Keinan, E. K. Hafeli, K. K. Seth, and R. Lamed, Thermostable enzymes in organic synthesis. 2. Asymmetric reduction of ketones with alcohol dehydrogenase from Thermoamerobium brockii, ]. Am. Chem. Sac., 108 162 (1986). 

Node, M., Nishide, K., Shigeta, Y., Shiraki, H., Obata, K. A Novel Tandem Michael Addition/Meerwein-Ponndorf-Verley Reduction Asymmetric Reduction of Acyclic a,P-Unsaturated Ketones Using A Chiral Mercapto Alcohol. J. Am. Chem. Soc. 2000, 122,1927-1936. 

Sakai, T., Yan, F., Kashino, S. and Uneyama, K. (1996) Asymmetric reduction of 2-(/V-ary-limino)-3,3,3-trifluoropropanoic acid esters leading to enantiomerically enriched 3,3,3-trifluo-roalanine. Tetrahedron, 52, 233-244. 

However, the use of an isopropyl or aromatic group reverses the sense of the asymmetric reduction. Thus, Alpine-Borane reduction of methyl 3-methyl-2-oxobutanoate gives methyl (f )-2-hydroxy-3-methylbutanoatc (10% cc) while reduction of ferf-butyl a-oxobcnzcncacctatc yields tert-butyl (K)-a-hydroxvbenzeneacetate (92% ec). 

Asymmetric reduction of ketones. Highly pure reagent can be prepared by hydroboration of ( + )-a-pinene either with borane-THF or with borane-dimethyl sulfide. The latter method is somewhat more convenient since borane-dimethyl sulfide is available commercially (Aldrich) and since reductions with reagent prepared in this way are more rapid than reductions with reagent prepared with BHq-THF. Reagent prepared by either method reduces ketones of the type R C0CH3 to R CH0HCH3 with optical yields of H. C. Brown and A. K. Mandal, J. Org 42, 2996 (1977). 

Asymmetric reduction of the ketone gives the chiral alcohol shown below. The larger (conjugated) side of the ketone sits in the less-hindered position (Rl as described in Section 7.3.7, Scheme 7.100). See Y. Kita, K. Higuchi, Y. Yoshida, K. lio, S. Kitagaki, K. Ueda, S. Akai and H. Fujioka, J. Am. Chem. Soc., 123 (2001), 3214. 

Molvinger, K., Lopez, M., Court, J. (1999) Asymmetric reduction and hydrogenation over heterogeneous catalysts prepared by reacting nickel-boride with norephedrine, J. Mol. Catal. A. Chem. 150,261-213. 

Takahashi, F., Tomii, K. and Takahashi, H. (1986) The electrochemical asymmetric reduction of alpha-V.eto acids in the magnetic-fields, Electrochem. Acta 31, 127-130. 

K. Hatton, K. Takahashi, M. Uematsu, N. Sakai, Multiple interactions between host cyclodextrin and guest compound assisting asymmetrically selective reduction with NaBH4 in aqueous media, Chem. Lett., 1990, 19, 1463-1466 K. Hattori, K. Takahashi, N. Sakai, Enantioface differentiating reduction of keto-acid in the presence of 6-deoxy-6-amino-j3-cyclodextrin with NaBHi in aqueous media. Bull. Chem. Soc. Jpn., 1992,65,2690-2696 K. Hattori, K. Takahashi, Asymmetric reduction of prochiral inclusion complex in aqueous media, Supramol. Chem., 1993, 2, 209-213. 

K. Takahashi, H. Yokomizo, K. Ishiyama, M. Kitsuta, M. Ohashi, New aspects of cyclodextrin chemistry induced by outside type complex formation asymmetric reduction of indol-3-pyruvic acid with NaBH4, J. Incl. Phenom. Macrocyc. Chem., 2006, 56, 95-99. 

Ap-24 Gibian, H., Kieslich, K., Koch, H. J., Kosmol, H., Rufer, C., Schroder, E., and Vossing, R., Tetrahedron Letters 21. 2321 (1966). Asymmetric reduction with Saccharomyces sp. and Bacillus thuringlensis of a carbonyl group in a totally synthetic, optically inactive steroid precursor. 

---