(Benzyloxy)<1-D1>acetaldehyd | 115463-94-0

• 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: (Benzyloxy)<1-D1>acetaldehyd
• 英文别名: 2-benzyloxy-(1-2H)acetaldehyde；O-benzyl<1-²H1>glycolaldehyde；2-(benzyloxy)acetaldehyde-1-d；1-Deuterio-2-phenylmethoxyethanone
• CAS: 115463-94-0
• 化学式: C₉H₁₀O₂
• 分子量: 151.169
• InChiKey: NFNOAHXEQXMCGT-RAMDWTOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Benzyloxy)<1-D1>acetaldehyd 在 baker's yeast 作用下， 以 乙醇 为溶剂， 反应 24.0h， 以51%的产率得到(+)-(S)-2-(benzyloxy)(1-2H)ethanol
  参考文献：
  名称：

  醋杆菌转化2-苯氧基乙醇转化为苯酚和乙醛的立体化学。

  摘要：

  厌氧细菌醋杆菌将2-苯氧基乙醇转化为苯酚和乙酸盐。LuPhet1菌株通过乙醛行进，同时H原子从乙醇部分的C（1）迁移到C（2）。通过化学合成方法制备的（R）-和（S）-2-苯氧基（1-2 H）乙醇的单独进料实验表明，参与1,2移位的H原子是pro-S之一酒精功能的对映体对。

  DOI：

  10.1002/hlca.200390212
• 作为产物：
  描述：

  2-苯基甲氧基乙酸甲酯 在 lithium aluminium deuteride 作用下， 生成 (Benzyloxy)<1-D1>acetaldehyd
  参考文献：
  名称：

  On the Early Steps of Cineol Biosynthesis in Eucalyptus globulus

  摘要：

  Samples of [4-H-2(1)]-1-deoxyxylulose (17a) and [2-C-13, 4-H-2(1)]-1-deoxyxlulose (17b), have been prepared by modification of known procedures and fed in aqueous solution to twiglets of Eucalyptus globulus. The probes of cineol (6) isolated from these experiments were analyzed by GC/MS, H-2- and C-13-NMR techniques. In the experiments with lm, the formation of five isotopomers of 6 could be detected. Their structure and relative abundance demonstrate that the C-13-label is incorporated to the same extent into the two C-5-units of 6, and that the H-2 label is retained to an extent of 57% in the starter dimethylallyl-diphosphate unit (DMAPP; 12), but completely or almost completely lost in the unit derived from isopentenyl diphosphate (IPP; 11), in the elongation step which leads to geranyl diphosphate (GPP; 1). These results confirm that the recently discovered mevalonate-independent pathway to IPP and DMAPP is operative in the biosynthesis of cineol, and indicate, together with previous finding, that, within this pathway, formation of IPP and DMAPP occurs in independent rather than in sequential steps. In addition, the demonstration of different metabolic origins for the olefinic H-atoms of GPP (1), the aliphatic C-10-precursor of 6, paves the way for a realistic interpretation of the strikingly consistent but hitherto unexplained anomalies detected in the natural-abundance H-2-NMR spectra of (+)- and (-)-alpha-pinene and of (+)-limonene.

  DOI：

  10.1002/1522-2675(20000906)83:9<2504::aid-hlca2504>3.0.co;2-z

文献信息

• Alkyne-Aldehyde Reductive CC Coupling through Ruthenium-Catalyzed Transfer Hydrogenation: Direct Regio- and Stereoselective Carbonyl Vinylation to Form Trisubstituted Allylic Alcohols in the Absence of Premetallated Reagents
  作者：Joyce C. Leung、Ryan L. Patman、Brannon Sam、Michael J. Krische

  DOI：10.1002/chem.201101554

  日期：2011.10.24

  Nonsymmetric 1,2‐disubstituted alkynes engage in reductive coupling to a variety of aldehydes under the conditions of ruthenium‐catalyzed transfer hydrogenation by employing formic acid as the terminal reductant and delivering the products of carbonyl vinylation with good to excellent levels of regioselectivity and with complete control of olefin stereochemistry. As revealed in an assessment of the

  非对称 1,2-二取代炔烃在钌催化的转移氢化条件下通过使用甲酸作为末端还原剂并以良好至优异的区域选择性和完全烯烃立体化学的控制。正如对钌抗衡离子的评估所揭示的，碘化物在指导 C  C 键形成的区域选择性方面起着至关重要的作用。同位素标记研究证实了可逆催化炔丙基 C  H 在 C  C 偶联之前的氧化加成，并证明 C C 偶联产物不会通过烯酮中间体进行可逆脱氢。这种转移氢化协议能够在没有化学计量金属试剂的情况下进行羰基乙烯基化。
• Rhodium-Catalyzed Asymmetric [2+2+2] Cyclization of 1,6-Enynes and Aldehydes
  作者：Mana Ishida、Yu Shibata、Keiichi Noguchi、Ken Tanaka

  DOI：10.1002/chem.201102418

  日期：2011.11.4

  Asymmetric catalysis: The rhodium‐catalyzed asymmetric [2+2+2] cyclization of 1,6‐enynes and aldehydes was achieved by using a cationic rhodium(I)/(R)‐binap complex as a catalyst (see scheme; cod=1,5‐cyclooctadiene). Coordination of the substrate heteroatom to the cationic rhodium plays an important role in this cyclization reaction.

  不对称催化：通过使用阳离子铑（I）/（R）-binap络合物作为催化剂，实现铑催化的1,6-炔烃和醛的不对称[2 + 2 + 2]环化反应（请参见方案； cod = 1,5-环辛二烯）。底物杂原子与阳离子铑的配位在该环化反应中起重要作用。
• C–H Bond Cleavage Is Rate-Limiting for Oxidative C–P Bond Cleavage by the Mixed Valence Diiron-Dependent Oxygenase PhnZ
  作者：Simanga R. Gama、Becky Suet Yan Lo、Jacqueline Séguin、Katharina Pallitsch、Friedrich Hammerschmidt、David L. Zechel

  DOI：10.1021/acs.biochem.9b00145

  日期：2019.12.31

  three active site residues. Primary deuterium KIE values of 5.5 ± 0.3 for D(V) and 2.2 ± 0.4 for D(V/K) were measured with (R)-2-amino[1-2H1]-1-hydroxyethylphosphonic acid, indicating that cleavage of the C1-H bond of the substrate is rate-limiting. This step is also rate-limiting for PhnZ Y24F, as shown by a significant deuterium KIE value of 2.3 ± 0.1 for D(V). In contrast, a different reaction step

  PhnZ 利用混合价二铁 (II/III) 辅因子和 O2 氧化裂解 (R)-2-氨基-1-羟乙基膦酸的碳-磷键，形成甘氨酸和正磷酸盐。活性位点残基 Y24 和 E27 被提议用于介导底物的诱导拟合识别和 O2 对活性位点 Fe 离子之一的访问。H62 被提议在催化过程中使底物的 C1-羟基去质子化。动力学同位素效应 (KIE)、pH 速率依赖性和定点诱变被用来探测速率决定过渡态和这三个活性位点残基的作用。用 (R)-2-氨基[1-2H1]-1-羟乙基膦酸测量 D(V) 的初级氘 KIE 值为 5.5 ± 0.3，D(V/K) 的初级氘 KIE 值为 2.2 ± 0.4，表明底物的 C1-H 键是限速的。这一步也是 PhnZ Y24F 的速率限制，如 D(V) 的 2.3 ± 0.1 的显着氘 KIE 值所示。相比之下，不同的反应步骤似乎限制了 PhnZ E27A 和 H62A 变体的速率，其
• Hammerschmidt, Friedrich, Liebigs Annalen der Chemie, 1988, p. 955 - 960
  作者：Hammerschmidt, Friedrich

  DOI：——

  日期：——
• Biosynthesis of natural products with a phosphorus-carbon bond. 7. Synthesis of [1,1-2H2]-, [2,2-2H2]-, (R)- and (S)-[1-2H1](2-hydroxyethyl)phosphonic acid and (R,S)-[1-2H1](1,2-dihydroxyethyl)phosphonic acid and incorporation studies into fosfomycin in Streptomyces fradiae
  作者：Friedrich Hammerschmidt、Hanspeter Kaehlig

  DOI：10.1021/jo00007a022

  日期：1991.3

  Nondeuteriated and deuteriated 2-(benzyloxy)ethanols (8a-c) were transformed into (2-hydroxyethyl)phosphonic acids (12a-c). 8c was prepared from dimethyl 2,3-O-isopropylidene-L-tartrate. 12b,c were fed to Streptomyces fradiae and were incorporated into fosfomycin (2), which was converted to amino phosphonic acid (-)-13. (-)-13 derived from 12b,c contained 42% and 34% deuterium, respectively. (1,2-Dihydroxyethyl)phosphonic acid ((+/-)-29) was not incorporated into fosfomycin. (S)- and (R)-(2-hydroxy[1-H-2-1]ethyl)phosphonic acids ((S)- and (R)-34) were prepared from (S)-2-(benzyloxy)[1-H-2-1]ethanol ((S)-30) and fed to S. fradiae. The deuterium of (R)-34 was lost, and the deuterium of (S)-34 was retained on incorporation into fosfomycin. The optical purity of (S)- and (R)-34 (84% and 86%, respectively) was determined by transformation to dimethyl ester and esterification with (+)-MTPA-Cl to afford 39b,c. 41 obtained from (S)-32 was identical with an authentic sample prepared from (S)-(2-amino[1-H-2-1]ethyl)phosphonic acid.