tert-butyldimethyl<(2-methyl-1,5-cyclohexadien-1-yl)oxy>silane | 101968-14-3

• 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: tert-butyldimethyl<(2-methyl-1,5-cyclohexadien-1-yl)oxy>silane
• 英文别名: 2-<(tert-butyldimethylsilyl)oxy>-1-methylcyclohexa-1,3-diene；tert-butyldimethyl((2-methylcyclohexa-1,5-dien-1-yl)oxy)silane；tert-butyldimethyl[(2-methyl-1,5-cyclohexadien-1-yl)oxy]silane；2-(tert-butyldimethylsilyloxy)-1-methyl-1,3-cyclohexadiene；Tert-butyl-dimethyl-(2-methylcyclohexa-1,5-dien-1-yl)oxysilane
• CAS: 101968-14-3
• 化学式: C₁₃H₂₄OSi
• 分子量: 224.418
• InChiKey: IOMRGFXBHPPQBB-UHFFFAOYSA-N

物化性质

• 沸点：
  235.1±8.0 °C(Predicted)
• 密度：
  0.88±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.63
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tert-butyldimethyl<(2-methyl-1,5-cyclohexadien-1-yl)oxy>silane 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 cerium(III) chloride 、 2,2-dimethyldioxirane 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 127.0h， 生成
  参考文献：
  名称：

  A remarkable cyclopropanation: the total synthesis of myrocin C

  摘要：

  DOI：

  10.1021/ja00047a079
• 作为产物：
  描述：

  6-methylcyclohex-2-en-1-one 、 叔丁基二甲硅基三氟甲磺酸酯 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以70%的产率得到tert-butyldimethyl<(2-methyl-1,5-cyclohexadien-1-yl)oxy>silane
  参考文献：
  名称：

  铑催化的乙烯基卡宾与二烯的对映选择性[4 + 2]环加成反应。

  摘要：

  在庞大的手性四羧酸二铜铑催化剂Rh2（Rp-PhTPCP）4存在下，2-甲硅烷氧基环1,3-二烯与E-乙烯基重氮乙酸酯的反应导致对映选择性[4 + 2]环加成反应，其中三个新的立体异构中心形成。[4 + 2]环加合物生成为具有高对映体控制（95-98％ee）的单一非对映异构体。当二烯包含另外的立体异构中心时，可以实现有效的动力学拆分。

  DOI：

  10.1002/anie.201914354

文献信息

• Regio- and stereoselectivity in Diels–Alder reactions of 1,2-disubstituted dienes with enantiopure (SS)-(p-tolylsulfinyl)-1,4-benzoquinones
  作者：M.Carmen Carreño、José L Garcı́a Ruano*、Cynthia Z Remor、Antonio Urbano

  DOI：10.1016/s0957-4166(00)00365-7

  日期：2000.11

  Reactions of 1,2-disubstituted dienes 1–3 with enantiopure sulfinylquinones 4–6 occur with similar π-facial diastereoselectivities but reversed regiochemistry under thermal conditions and in the presence of ZnBr2. After spontaneous elimination of the sulfoxide, optically active polycyclic dihydroquinones are formed with ees ranging from 36 to >97%. The regiochemistry of the process is controlled by

  的1,2-二取代的二烯反应1 - 3与对映体纯sulfinylquinones 4 - 6发生类似π-面部非对映选择性，但在热条件下和在ZnBr存在反转区域化学2。自发消除亚砜后，形成旋光性多环二氢醌，其ee含量为36％至> 97％。该方法的区域化学由热反应中C-1处的烷基取代基控制，而在ZnBr 2存在下，C-2处的氧化功能成为主要控制者。
• Ihara, Masataka; Ishida, Yohhei; Fukumoto, Keiichiro, Chemical and pharmaceutical bulletin, 1985, vol. 33, # 9, p. 4102 - 4105
  作者：Ihara, Masataka、Ishida, Yohhei、Fukumoto, Keiichiro、Kametani, Tetsuji

  DOI：——

  日期：——
• Total Synthesis of (.+-.)-Myrocin C
  作者：Margaret Y. Chu-Moyer、Samuel J. Danishefsky、Gayle K. Schulte

  DOI：10.1021/ja00104a002

  日期：1994.12

  A stereoselective total synthesis of racemic myrocin C (1) has been achieved. Initial investigations produced cyclopropane-containing AB sector 22 via intramolecular ester-tethered Diels-Alder reaction of quinone 14 followed by internal alkylation of bromide 19. Although the natural product was not to be obtained through this route, the information garnered from this impetus provided the basis for a strategically improved and ultimately successful synthesis of 1. Thus, intermolecular Diels-Alder reaction of p-benzoquinone with cyclic diene 39 gave endo cycloadduct 41 which could be elaborated to cyclopropane precursors 52 and 99. While a plethora of intramolecular alkylation reactions of derivatives of 52 failed to afford cyclopropane-containing products, a novel organolithium-induced cyclization reaction of 99 did indeed provide key compound 96 via postulated intermediate 100. The resultant functionality in 96 paved the way for a directed intramolecular Diels-Alder annulation of the C-ring and concomitant introduction of the remote quaternary C13 stereocenter (cf. 96 --> 107 --> 108). The tertiary hydroxyl group at C9 was then introduced via epoxidation of 119 followed by overall eliminative ring-opening (123 --> 125 --> 5). The incorporation of the C6 tertiary hydroxyl group was accomplished via oxidation of the enolate derived from 6-desoxymyrocin C (5), yielding racemic 1. Studies on the bioactivation process of 5 and 1 led to support for a hypothesis which emphasized the importance of the C6 hydroxyl group in facilitating cyclopropane-ring-opening possibly through the intermediacy of quinone homomethide 134.
• Application of Chiral Cationic Catalysts to Several Classical Syntheses of Racemic Natural Products Transforms Them into Highly Enantioselective Pathways
  作者：Qi-Ying Hu、Gang Zhou、E. J. Corey

  DOI：10.1021/ja046154m

  日期：2004.10.1

  This paper describes the application of chiral oxazaborolidinium cations of type 2 to various enantioselective Diels-Alder reactions that have served as early key steps for the syntheses of complex natural products. In the original syntheses these Diels-Alder reactions produced racemic adducts and led to racemic target molecules unless a separation of enantiomers by classical resolution was employed. By use of chiral catalysts of type 2, chiral products were obtained directly from Diels-Alder reactions of achiral components in excellent yield and enantioselectivity and with the mechanistically predicted absolute configuration. As a result, a number of classical syntheses could be converted to enantioselective versions, including (1) cortisone/cortisol (Merck/Sarett), (2) dendrobine (Kende), (3) vitamin B-12 (Eschenmoser), (4) myrocin C (Chu-Moyer/Danishefsky), (5) coriolin and hirsutene (Mehta), (6) dendrobatid 251F (Aube), (7) silphinene (Ito), and (8) nicandrenone core (Stoltz/Corey).
• IHARA, MASATAKA;ISHIDA, YOHHEI;FUKUMOTO, KEIICHIRO;KAMETANI, TETSUJI, CHEM. AND PHARM. BULL., 1985, 33, N 9, 4102-4105
  作者：IHARA, MASATAKA、ISHIDA, YOHHEI、FUKUMOTO, KEIICHIRO、KAMETANI, TETSUJI

  DOI：——

  日期：——