methyl O-tert-butyldimethylsilyl-N-(diphenylmethylene)-L-serinate | 131472-75-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl O-tert-butyldimethylsilyl-N-(diphenylmethylene)-L-serinate
• 英文别名: methyl O-(tert-butyldimethylsilyl)-N-(diphenylmethylene)-L-serinate；methyl (2S)-2-(benzhydrylideneamino)-3-[tert-butyl(dimethyl)silyl]oxypropanoate
• CAS: 131472-75-8
• 化学式: C₂₃H₃₁NO₃Si
• 分子量: 397.59
• InChiKey: KQLJTUWBOXHEMO-FQEVSTJZSA-N

物化性质

• 沸点：
  426.8±45.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.09
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl O-tert-butyldimethylsilyl-N-(diphenylmethylene)-L-serinate 在 吡啶 、 4-二甲氨基吡啶 、 potassium dioxotetrahydroxoosmate(VI) 、 i-Bu₂AlH*i-Bu₃Al 、 potassium carbonate 、 potassium hexacyanoferrate(III) 作用下， 以 水 、 甲苯 、 叔丁醇 为溶剂， 反应 29.33h， 生成 (2S,3R,4R,5S)-3,4,5-Triacetoxy-2--1-O-(tert-butyldimethylsilyl)hexan-1-ol
  参考文献：
  名称：

  Glycosidase Inhibitors:  Synthesis of Enantiomerically Pure Aza-Sugars from Schiff Base Amino Esters via Tandem Reduction-Alkenylation and Osmylation

  摘要：

  Nitrogen-in-the-ring "aza-sugars" have been synthesized in enantiomerically pure form from the amino acid L-alanine in excellent overall yield. The O'Donnell's Schiff base of L-alanine methyl ester 9a was converted to ate-sugar L-fuco-1-deoxy-nojirimycin, 18, and to the epimer L-gulo-1-deoxy-nojirimycin, 20, in eight steps. The overall yields were 20 and 29%, respectively. The methodology for the efficient generation of silyl- and benzyl-protected (E)-3-lithio-2-propen-1-ols, and the use of these alkenyllithiums with iBu(5)Al(2)H as nucleophiles in the three-selective tandem reduction-alkenylation of the Schiff base esters is described. Osmium-catalyzed cis-oxygenation of the resulting olefin products was selective for the galacto (fuco) amino polyols in all cases for the acyclic olefins, and was gulo-selective for the cyclic D-4,5-dihydropyridine pivalate, 17c. TEMPO-NaOCl was selective for oxidation of the primary position of the acyclic Schiff bases, and allowed for minimal protection/deprotection of the intermediates. The resulting N-benzhydryl heterocycles were easily deprotected with H-2-Pd at atmospheric pressure.

  DOI：

  10.1021/jo9820115
• 作为产物：
  描述：

  二苯甲酮亚胺 在 咪唑 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 methyl O-tert-butyldimethylsilyl-N-(diphenylmethylene)-L-serinate
  参考文献：
  名称：

  Aluminoxy acetals from .alpha.-amino esters: chirality transfer via sequential addition of hydride and C-nucleophiles. 2-Amino alcohols and sphingosines

  摘要：

  The reaction of alpha-imino esters (O'Donnell's Schiff bases) with aluminum hydrides to produce acetal-like intermediates and subsequent reaction with carbon nucleophiles has been studied. Treatment of optically pure imine-protected amino esters with iBu2AlH or iBuAlH.Bu3Al, followed by RMgX or RLi provided threo-2-amino alcohols in high yield (73-85%) and excellent ''syn'' stereoselectivity (8:1 to >20.1, threo or like product preferred). Use of nonpolar solvents (CH2Cl2-hexane) provided the highest stereoselectivities. Use of the less-reactive iBu2AlH.iBu3Al complex lowered the amount of undesired primary alcohol products observed. Thermally labile aluminoxy acetal intermediates were observed by H-1 NMR and were trapped with N-(trimethylsilyl)imidazole to produce relatively stable monosilyl acetals (mixed acetals). Alanine-derived Schiff bases 2a-e showed a correlation between the steric bulk of the ester and threo selectivity The presence of THF reduced this correlation, suggesting the C-nucleophile addition involves a Lewis acid-assisted S(N)2-like displacement of the aluminoxy acetal or displacement of a tight-ion pair. In addition to the synthesis of optically pure arylethanolamines 6a-d from representative amino acids, threo-sphingosines 8a-d were synthesized from L-serine-derived Schiff base 4b, and 1-deoxy-threo-sphingosines 9a-d were synthesized from L-alanine in a similar fashion. Experimental details are provided.

  DOI：

  10.1021/jo00046a032

文献信息

• β-Amino alcohols from amino acids: Chelation control via schiff bases.
  作者：Robin Polt、Matt A. Peterson

  DOI：10.1016/s0040-4039(00)97784-0

  日期：1990.1

  Sequential addition of iBu2AIH and RLi or RMgX to Schiff base esters derived from amino acids provides a simple route to β-amino alcohols. The reaction procedes without racemization, and with high threo selectivity. Several representative sphingosines are synthesized.

  将iBu 2 AIH和RLi或RMgX顺序添加到衍生自氨基酸的席夫碱酯中，提供了一条通往β-氨基醇的简单途径。反应进行时没有外消旋化，并且具有高苏式选择性。合成了几种代表性的鞘氨醇。
• Preparation of Monosilyl Acetals from Esters via iBu2AlH Reduction and Trapping with N-(Trimethylsilyl)imidazole. Addition of Allyltrimethylsilane To Yield Homoallylic Alcohols or Ethers
  作者：Dalibor Sames、Yunqi Liu、Lynn DeYoung、Robin Polt

  DOI：10.1021/jo00112a039

  日期：1995.4

  Alkyl esters were reduced with iBu(2)AlH or a 1:1 mixture of iBu(2)AlH and iBu(3)Al (iBu(2)AlH . iBu(3)Al or iBu(5)Al(2)H), followed by trapping of the resulting tetrahedral intermediate with TMS-imidazole to produce monosilyl acetals. Reaction of the mixed acetals with allyltrimethylsilane in the presence of Lewis acids (Hosomi-Sakurai reaction) generated homoallylic alcohols or ethers selectively, depending on the substitution of the monosilyl acetal. TMS methoxy acetals (MeO-CH-OTMS) and TMS ethoxy acetals bearing additional complexing groups such as MeO- or Ph(2)C=N- provided alcohols with 1.5:1-9:1 threoselectivity, while simple TMS ethoxy acetals provided only ethyl ethers as products. The monosilyl acetal configuration was easily epimerized or racemized, and the configuration of the Hosomi-Sakurai product was apparently independent of the initial monosilyl acetal reactant configuration.
• Glycosyltransferase Inhibitors:  Synthesis of <scp>d</scp>-<i>threo</i>-PDMP, <scp>l</scp>-<i>threo</i>-PDMP, and Other Brain Glucosylceramide Synthase Inhibitors from <scp>d</scp>- or <scp>l</scp>-Serine
  作者：Scott A. Mitchell、Bryan D. Oates、Hossein Razavi、Robin Polt

  DOI：10.1021/jo980951j

  日期：1998.11.1

  The synthesis of enantiomerically pure (1S,2S)-1-phenyl-2-decanoylamino-3-N-morpholino-1- propanol (L-threo-PDMP) (la) from L-serine, and the enantiomer (1R,2R)-1-phenyl-2-decanoylamino-3-morpholino-1-propanol (D-threo-PDMP] (Ib) from D-serine is reported. Reductive alkylation of the fully protected O'Donnell's Schiff base (3b) derived from D-serine provided the beta-amino alcohol 5b in high yield and excellent selectivity, which yielded optically pure Ib in high yield after six steps. Three other D-threo-PDMP analogues with various amine groups have been synthesized using the same methodology, including the more potent pyrrolidine compound D-threo-PDPP (le). A key feature of the synthesis is the isolation of tosylate (8b), which allows for the divergent synthesis of many analogues from a common advanced intermediate. The synthesis is amenable to large-scale production of D-threo-PDMP, L-threo-PDMP, and similar compounds.
• POLT, ROBIN;PETERSON, MATT A., TETRAHEDRON LETT., 31,(1990) N5, C. 1985-1986
  作者：POLT, ROBIN、PETERSON, MATT A.

  DOI：——

  日期：——
• An Enantioselective Synthesis of N-Methylfucosamine via Tandem C-C/C-O Bond Formation
  作者：Dalibor Sames、Robin Polt

  DOI：10.1021/jo00095a039

  日期：1994.8

  Optically pure D-(+)-N-methylfucosamine (8) has been synthesized from a TBDMS-protected methyl L-serinate benzophenone Schiff base (O'Donnell's Schiff base, 1) in seven steps in 13% overall yield. Efficient construction-of the requisite amino triol acetate 3a with the proper stereochemical configuration is accomplished in two steps with a chelation-controlled reduction-alkylation reaction using \Bu(2)AlH.Al-iBu(3)/E-LiCH=CHCH3, followed by oxidation with OsO4. Conversion of the Schiff base to the N-benzhydryl protecting group and methylation (Eschweiler-Clark) is accomplished in one pot with NaCNBH3 in ti;e presence of H2C=O. Deprotection and oxidation of the primary alcohol, followed by deacetylation with KCN, provided the desired product 8.