Tin- or magnesium-mediated diastereoselective aldol-type reactions for the asymmetric synthesis of α-substituted serines

Sano, Shigeki; Miwa, Takeshi; Liu, Xiaokai; Ishii, Takahiro; Takehisa, Tomoka; Shiro, Motoo; Nagao, Yoshimitsu

doi:10.1016/s0957-4166(98)00371-1

Cited by 19 publications

(4 citation statements)

References 7 publications

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“…Diethyl N-Cbz-2-aminomalonate 2 was prepared from diethyl 2-aminomalonate hydrochloride 1 by a standard method in 97% yield [6]. Then diethyl N-Cbz-2-alkyl-2-aminomalonates 3a-d were obtained by the treatment of N-protected diester 2 with NaH, followed by alkylation of the resulting sodium enolate with alkyl halides in 77-88% yields.…”

Section: Resultsmentioning

confidence: 99%

“…Thus, the asymmetric synthesis of -substituted serines has been an area of intensive investigation in our laboratory for the past few years. As part of our own contribution to this area, we developed several non-enzymatic asymmetric syntheses based on novel bislactim ethers derived from diethyl aminomalonate hydrochloride [6]. Further, we applied a chemo-enzymatic *Address correspondence to this author at the Graduate School of Pharmaceutical Sciences, The University of Tokushima, Sho-machi, Tokushima 770-8505, Japan; Tel: +81-88-633-7273; Fax: +81-88-633-9503; E-mail: ssano@ph.tokushima-u.ac.jp synthesis of -substituted serines utilizing enzyme-catalyzed desymmetrization of -symmetric compounds [7].…”

Section: Introductionmentioning

confidence: 99%

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Chemoenzymatic Synthesis of α-Substituted Serines via Enantiodivergent Transformation

Sano¹,

Nakao²,

Takeyasu³

et al. 2009

TOOCJ

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A series of (R)-N-Cbz-2-alkyl-2-amino-3-hydroxypropyl acetates was prepared by enzymatic acetylation of NCbz-2-alkyl-2-aminopropane-1,3-diols with immobilized lipoprotein lipase from Pseudomonas sp. in up to 98% enantiomeric excess (ee). Enantiodivergent oxidation of (R)-N-Cbz-2-alkyl-2-amino-3-hydroxypropyl acetates readily furnished (R)-and (S)--substituted serines ( -benzylserines and -methylserines). Enzymatic hydrolysis of diethyl N-Cbz-2-amino-2-methylmalonate catalyzed by porcine liver esterase afforded (R)-N-Cbz-2-amino-3-ethoxy-2-methyl-3-oxopropanoic acid in 97% ee. (R)-N-Cbz-2-amino-3-ethoxy-2-methyl-3-oxopropanoic acid was also transformed to both enantiomers of -methylserine via enantiodivergent reduction.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Chemoenzymatic Synthesis of α-Substituted Serines via Enantiodivergent Transformation

Sano¹,

Nakao²,

Takeyasu³

et al. 2009

TOOCJ

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“…In previous studies, we have reported aldol-type reactions with magnesium salts in the presence of amines and shown the unique stereo-and chemoselectivity. [1][2][3][4][5][6] In the course of study, we were interested in the effects of magnesium salts by differences in the counter anions and the effects of the amines. It is known that the counter anions of metal salts and amines affect the reactivity and/or selectivity in some aldoltype reactions.…”

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Effects of Magnesium Salts and Amines on the Stereoselectivity in the Imine Aldol Reaction

et al. 2007

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“… "Asymmetrization"という独創的な新概念である． [1][2][3] 本反応設計に際しては，プロキラルな s 対称性ジカルボン酸分子，アミドカルボニル基とチオカルボニル基間の双極子-双極子反発，活性アミド構造等の分子構造特性を活用した． [16][17][18][19][20] a 置換セリン部を有する生理活性天然物として…”

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分子構造特性を基盤とする新反応の開発並びに薬学的応用研究

Nagao

2002

YAKUGAKU ZASSHI

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The author and his group have been developing new reactions based on molecular structure characteristics; s symmetric bifunctional molecules, dipole-dipole repulsion, active amide structures, latent active species, orbital-orbital interactions, nonbonded interactions, strained structures, allenic structures, etc. Various new reactions such as asymmetric aminolyses and Dieckmann-type cyclizations of prochiral s symmetric dicarboxylic diamides, asymmetric aldol-type reactions onto g hydroxybutenolides and asymmetric imine alkylations onto v acetoxy lactams using chiral Sn(II) enolates, asymmetric Pummerer-type reactions, cascade reactions and endo-mode cyclizations exploiting a,b unsaturated allenic esters and ketones, base-and palladium-promoted ring-expansion reactions, and syntheses of a substituted serines and 1 azabicyclo[1.1.0]butane have been achieved. These new reactions were applied to the synthetic development of new seed and lead compounds (SH enzyme inhibitors, tumor inhibitors, and antibiotics ) with the aim of synthesizing new drugs. Asymmetric syntheses of (＋) Prelog Djerassi lactonic acid methyl ester, (＋) carbacyclin, ISP I (myriocin), (＋) conagenin, Geissman-Waiss lactone, biapenem (a new carbapenem antibiotic), thienamycin-like g lactam, and bicyclic alkaloids were also achieved by utilizing these reactions. Evaluation and molecular design of the seed and model compounds for angiotensin II receptor antagonists, tumor inhibitors, and antibiotics have been investigated on the basis of QRSA and/or nonbonded S…X (X＝O, N, S, halogens) interaction concepts.

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Tin- or magnesium-mediated diastereoselective aldol-type reactions for the asymmetric synthesis of α-substituted serines

Cited by 19 publications

References 7 publications

Chemoenzymatic Synthesis of α-Substituted Serines via Enantiodivergent Transformation

Chemoenzymatic Synthesis of α-Substituted Serines via Enantiodivergent Transformation

Effects of Magnesium Salts and Amines on the Stereoselectivity in the Imine Aldol Reaction

分子構造特性を基盤とする新反応の開発並びに薬学的応用研究

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