(2S,3R)-2-methyl-3-<(triethylsilyl)oxy>pentanal | 77405-44-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (2S,3R)-2-methyl-3-<(triethylsilyl)oxy>pentanal
• 英文别名: (2S,3R)-2-methyl-3-triethylsilyloxypentanal
• CAS: 77405-44-8
• 化学式: C₁₂H₂₆O₂Si
• 分子量: 230.423
• InChiKey: OOQJYAGTLZENRF-VXGBXAGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.62
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 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：

  (2S,3R)-2-methyl-3-<(triethylsilyl)oxy>pentanal 在 吡啶 、 氢氧化钾 、 sodium tetrahydroborate 、 Pyr*CrO₃*HCl 、 sodium acetate 、 三氟甲烷磺酸亚铜(I)苯联合体 (2:1) 、 溶剂黄146 、 N,N-二异丙基乙胺 、 三氟乙酸 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 乙腈 、 叔丁醇 、 苯 为溶剂， 反应 52.5h， 生成 6-脱氧红霉内酯B
  参考文献：
  名称：

  Total synthesis of 6-deoxyerythronolide B

  摘要：

  DOI：

  10.1021/ja00396a051
• 作为产物：
  描述：

  (4S)-3-<(2'S,3'S)-3'-((triethylsilyl)oxy)-2'-methylpentanoyl>-4-isopropyl-1,3-oxazolidin-2-one 在 吡啶 、 氯化亚砜 、 二异丁基氢化铝 、 二甲基亚砜 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 1.58h， 生成 (2S,3R)-2-methyl-3-<(triethylsilyl)oxy>pentanal
  参考文献：
  名称：

  Strategies for Macrolide Synthesis. A Concise Approach to Protected Seco-Acids of Erythronolides A and B

  摘要：

  Concise syntheses of protected derivatives of the seco-acids of erythronolides A and B, 5 and 6, respectively, have been completed wherein the longest linear sequence requires only 13 chemical steps from 5-ethylfuraldehyde (15). The syntheses commenced with the asymmetric aldol condensation of 15 according to the Evans protocol to afford the optically pure syn adduct 16, thereby establishing the critical stereocenters at C(4) and C(5) of the erythromycin backbone. Reductive removal of the chiral auxiliary from 16 gave the diol 17, which was converted to the bicyclic enone 18 by an one-pot process involving sequential oxidation of the furan ring and acid-catalyzed bicycloketalization. Stereoselective elaboration of 18 to the tertiary alcohol 19 was achieved in two steps by sequential treatment with lithium dimethylcuprate and methyllithium in the presence of cerium trichloride. Compound 19 underwent facile acid-catalyzed reorganization to the isomeric ketal 21, which was transformed into 24 by a Swern oxidation and a second asymmetric aldol condensation. However, the necessary refunctionalization of 24 into a ketone that would participate in the requisite aldol reaction to append the C(11)-C(15) segment of the erythronolide backbone could not be induced. On the other hand, transthioketalization of 19 gave the triol 26, which was converted to 28 by the thermodynamically-controlled formation of an acetonide of the 1,2-diol array. Deprotection of the C(9) ketone function followed by Swern oxidation produced the keto aldehyde 31, which underwent chemoselective, Lewis acid-mediated addition of tri-n-butylcrotylstannane to the aldehyde function to furnish a mixture (4:1) of the homoallylic alcohols 32 and 33; the major product 32 comprises the C(1)-C(10) subunit common to the seco-acids of both erythronolides A and B. Diastereoselective aldol condensation of the enolate derived from 32 with 40 gave 42 as the major adduct; oxidative processing of the terminal olefin then delivered the erythronolide B seco-acid derivative 46. The proposed structure of 42 was initially based upon its conversion into the polyol 48, which was identical to that derived from natural erythronolide B (49). Subsequent to this chemical correlation, the X-ray structure of 50, which was prepared from 42, unequivocally verified this assignment. In experiments directed toward the preparation of the seco-acid of erythronolide A, the directed aldol reactions of 32 with the aldehydes 59 and 60 were examined. Although the addition of the enolate of 32 to 59 produced none of the requisite adduct, its reaction with 60 gave a mixture (1:5) of 62 and 64. Stereoselective reduction of the C(9) carbonyl function of 62 followed by oxidative cleavage of the double bond and global deprotection gave the polyol 62, which was identical with the polyol derived from natural erythromycin A (1).

  DOI：

  10.1021/ja00090a016

文献信息

• Triple asymmetric synthesis for fragment assembly: Validity of approximate multiplicativity of the three diastereofacial selectivities
  作者：Allen J. Duplantier、Michael H. Nantz、John C. Roberts、Robert P. Short、Peter Somfai、Satoru Masamune

  DOI：10.1016/s0040-4039(00)70696-4

  日期：1989.1

  A strategy of triple asymmetric synthesis is illustrated to be effective for stereochemical control in fragment assembly, a task often encountered in convergent natural product synthesis. The stereochemical outcome of aldol reactions involving three chiral components supports a rule of approximate multiplicativity of facial selectivities intrinsic to the chiral reactants involved in each reaction.

  说明了三重不对称合成的策略对于片段组装中的立体化学控制是有效的，这是会聚天然产物合成中经常遇到的任务。涉及三个手性组分的醛醇缩合反应的立体化学结果支持了涉及每个反应的手性反应物固有的面部选择性的近似多重性的规则。
• Macrolide synthesis: narbonolide
  作者：Tatsuo Kaiho、Satoru Masamune、Tatsuo Toyoda

  DOI：10.1021/jo00347a061

  日期：1982.4