α-(triethylsilyl)propionaldehydr tert-butylimine | 99405-12-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: α-(triethylsilyl)propionaldehydr tert-butylimine
• CAS: 99405-12-6
• 化学式: C₁₃H₂₉NSi
• 分子量: 227.465
• InChiKey: YNHITDCCYJWRRH-SDNWHVSQSA-N

物化性质

• 沸点：
  54-55 °C(Press: 0.22 Torr)
• 密度：
  0.79±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.75
• 重原子数：
  15.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  12.36
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  3-tert-butyldimethylsilyloxy-2-methylpropanal 、 α-(triethylsilyl)propionaldehydr tert-butylimine 生成 5-[tert-butyl(dimethyl)silyl]oxy-2,4-dimethylpent-2-enal
  参考文献：
  名称：

  分子内烯丙基锡烷-羰基缩合。乙烯基环丙烷衍生物和不寻常的二聚体产物的形成

  摘要：

  已经观察到烯丙基锡烷部分与通过一个碳链连接的羰基之间的分子内缩合反应，得到甲硅烷氧基乙烯基环丙烷。在一种情况下形成了意外的二聚产物。醛衍生的乙烯基环丙烷已扩环成环戊烯醇。

  DOI：

  10.1016/s0040-4039(00)60636-6
• 作为产物：
  描述：

  三乙基氯硅烷 、 N-(propylidene)-tert-butylamine 在 lithium diisopropyl amide 作用下， 生成 α-(triethylsilyl)propionaldehydr tert-butylimine
  参考文献：
  名称：

  醛的乙烯基化：一种改进的制备α甲酰基亚乙基三苯基磷烷的方法，以及一种改进的丙醛的α甲硅烷基亚胺试剂

  摘要：

  据报道，由碘代乙基三苯基phosph和甲酸乙酯可高产率地制备α-甲酰基亚乙基三苯基磷烷。丙醛的α-三乙基甲硅烷基叔丁基亚胺是一种热稳定且易于纯化的试剂，可平滑地烯化醛和酮。

  DOI：

  10.1016/s0040-4039(00)94835-4

文献信息

• Total synthesis of (5S)-thiolactomycin: revision of the absolute configuration of the natural product
  作者：Mark S. Chambers、Eric J. Thomas

  DOI：10.1039/c39890000023

  日期：——

  (5S)-Thiolactomycin (1) has been synthesized and found to be laevorotatory, [α]D20–172°(c 0.2, MeOH); the dextrorotatory natural product, [α]D20+176°(c 1.0, MeOH), is therefore the (5R)-enantiomer.

  已合成（5 S）-硫霉素（1），发现它是催乳的，[α] D 20 –172°（c 0.2，MeOH）; 因此，右旋天然产物[α] D 20 + 176°（c 1.0，MeOH）为（5 R）-对映体。
• A highly selective method for the synthesis of(E)-α-methyl-α,β-unsaturated aldehydes
  作者：R. Desmond、S.G. Mills、R.P. Volante、I. Shinkai

  DOI：10.1016/s0040-4039(00)80374-3

  日期：1988.1
• Enantioselective synthesis of the bottom half of chlorothricolide. 3. Studies of the steric directing group strategy for stereocontrol in intramolecular Diels-Alder reactions
  作者：William R. Roush、Masanori Kageyama、Renata Riva、Bradley B. Brown、Joseph S. Warmus、Kevin J. Moriarty

  DOI：10.1021/jo00003a049

  日期：1991.2

  The intramolecular Diels-Alder reactions of a series of C(7)-alkoxy-substituted 2(E),8(Z),10(E)-undecatrienoates and trienals containing removable C(9)-Br or C(9)-SiMe3 substituents (11, 12, 13, 33, 42, 43, 44, 45) were studied as part of a program directed toward the total synthesis of the bottom half of chlorothricolide. The IMDA reaction of trienoate 3 that lacks a C(9) substituent had previously been shown to cyclize with poor stereoselectivity to a mixture of four cycloadducts. It was expected that the IMDA reactions of trienes containing C(9) substituents (i.e., steric directing groups) would proceed with substantially enhanced stereoselectivity via trans-fused transition state A owing to nonbonded interactions that the steric directing groups experience in the competitive transition states B-D. Cis-fused transition states C and D suffer from serious interactions between C(9)-X and the axial C(6)-H, while trans-fused transition state B is destabilized by a 1,3-eclipsing interaction with the C(7)-alkoxyl group. Only the desired transition state, trans-fused transition state A, suffers from no serious interactions involving the C(9) steric directing group. These predictions were verified experimentally: the trans-fused cycloadduct deriving from A was the major product in all cases. Stereoselectivity for trans-fused cycloadducts was consistently greater, using C(9)-TMS directing groups compared to C(9)-Br substituted systems (for IMDA reactions under analogous conditions), but the C(9)-Br group appeared to have a greater influence on the partition between transition states A and B (see Table I). A surprising aspect of this study, however, is that significant amounts of cis-fused cycloadducts were obtained from the thermal cyclizations of the above-named trienes (12-45%), and this pathway was not entirely suppressed even in the Lewis acid catalyzed cycloadditions of trienals 44 and 45 (5-9% of cis fused cycloadduct). The results with TMS-substituted trienes 33, 42, and 44 thus are in disagreement with an earlier report by Boeckman and Barta (ref 5f) that the IMDA reaction of 33 gives ''a single cycloadduct (> 100:1).'' The cis-fused diastereomers most probably arise via boat-like transition state E rather than the chair-like transition state C. Cis-fused cycloadducts were not observed in the IMDA reaction of TMS-substituted triene 61 that lacks a C(7)-alkoxy substituent, suggesting that the C(7)-alkoxy groups electronically deactivate trans-fused transition state A such that boat-like transition state E is competitive only with substrates containing such C(7)-alkoxy substituents. Data are also presented that show that the C(9)-TMS substituents lead to an increase in reactivity (e.g., the IMDA reaction of 61 that proceeds at ambient temperature and the acid-catalyzed cyclocondensation of TMS diene aldehyde 63). This study defines bromo trienoate 43 as the optimal precursor to the bottom half unit (2) of chlorothricolide, even though the IMDA reaction of 43 is less selective than that of TMS-substituted trienes 42 and 44. The synthesis of 43 (Figure 4) involving the Pd0-catalyzed cross-coupling reaction of dibromo olefin 35 and vinylboronate 37 is shorter and considerably more efficient than the syntheses of TMS trienes 42 and 44, and this compensates for the fact that 43 is the least selective IMDA substrate.Syntheses that proceed by way of TMS trienoates like 42 or TMS trienals like 44 become competitive only if a more efficient triene synthesis is devised.
• Synthesis of a C22-34 Subunit of the Immunosuppressant FK-506
  作者：James A. Marshall、Shiping Xie

  DOI：10.1021/jo00127a031

  日期：1995.11

  A new route to the C22-34 subunit of FK-506 was developed. A highly diastereoselective Diels-Alder reaction of 1,3-butadiene with the bis-acrylate of (R,R)-hydrobenzoin and subsequent saponification provided the cyclohexenecarboxylic acid 6.4 of 95% ee. Elaboration to the enal 9.2 was effected by known transformations. Enal 9.2 underwent diastereoselective and enantiospecific S(E)2' addition of allenyl stannane (S)-3.9 affording the homopropargylic alcohol 9.3 as an 85:15 syn/anti mixture. The PMB ether 9.5 was converted to the known benzylidene derivative 10.4 by sequential treatment with Red-Al, epoxidation, a second reduction with Red-Al, and oxidative benzylidene formation with DDQ.
• Experimental and Theoretical Analysis of the Steric Tolerance of the Binding Site of Bacterioopsin with the Use of Side-Chain Methyl-Shifted Retinal Analogs
  作者：Angel R. de Lera、Beatriz Iglesias、Jesus Rodriguez、Rosana Alvarez、Susana Lopez、Xavier Villanueva、Esteve Padros

  DOI：10.1021/ja00136a021

  日期：1995.8

  Four positional isomers of trans-retinal (1) differing in the location of the side-chain methyl groups have been prepared by a combination of Wittig and highly stereocontrolled Suzuki coupling reactions. The incubation of 9-demethyl-10-methylretinal (5) with bacterioopsin yielded an artificial pigment with an opsin shift of 4630 cm(-1) The other three analogs, namely 13-demethyl-14-methylretinal (3), 13-demethyl-12-methylretinal (4), and 9-demethyl-8-methylretinal (6) did not bind to the apoprotein. In order to rationally address the intrinsic structural differences among analogs which could be relevant to the discrimination exhibited by the protein binding site, ab initio calculations with complete optimization at the 3-21G level were performed on model N-methylretinal iminium salts derived from aldehydes 1 and 3-6. The validity of the approach was inferred from the remarkable coincidence between the minimized structure of N-methylretinal Schiff base (PSB-1) and the structural parameters displayed by N-methyl-N-phenylretinal iminium perchlorate (38b). Computations clearly show that the location of the methyl groups on the polyene side chain is of the utmost importance in determining the overall shape of the retinal ligands. Those structural effects, added to the dominant steric and electronic restrictions of the binding pocket, would explain the observed discrimination among the analogs 3-6, with minor structural changes, and perhaps among other retinals reported in the literature. Additionally, the theoretical and experimental results obtained with 9-demethyl-8-methylretinal (6) provide further indirect evidence of the importance of the 6-s-trans conformation for the native chromophore in bacteriorhodopsin.