tert-butyl 4-(2-bromoethylidene)piperidine-1-carboxylate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: tert-butyl 4-(2-bromoethylidene)piperidine-1-carboxylate
• 化学式: C₁₂H₂₀BrNO₂
• 分子量: 290.2
• InChiKey: NMMONRANLRERGP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-butyl 4-(2-bromoethylidene)piperidine-1-carboxylate 在 sodium hydride 、 碳酸氢钠 、 戴斯-马丁氧化剂 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 17.0h， 生成 tert-butyl 4-(2-((4-methyl-N-(4-oxobutyl)phenyl)sulfonamido)ethylidene)piperidine-1-carboxylate
  参考文献：
  名称：

  Visible-Light-Promoted Intramolecular α-Allylation of Aldehydes in the Absence of Sacrificial Hydrogen Acceptors

  摘要：

  We report herein an unprecedented protocol for radical cyclization of aldehydes with pendant alkenes via synergistic photoredox, cobaloxime, and amine catalysis. The transformation was achieved in the absence of external oxidants, providing a variety of 5-, 6-, and 7-membered ring products with alkene transposition in satisfactory yields. The reaction exhibits wide functional group compatibility and occurs under mild conditions with extrusion of H-2.

  DOI：

  10.1021/acs.orglett.0c02742
• 作为产物：
  描述：

  2-(1-BOC-哌啶-4-基)乙醇 在 三溴化磷 作用下， 以 乙醚 为溶剂， 生成 tert-butyl 4-(2-bromoethylidene)piperidine-1-carboxylate
  参考文献：
  名称：

  Visible-Light-Promoted Intramolecular α-Allylation of Aldehydes in the Absence of Sacrificial Hydrogen Acceptors

  摘要：

  We report herein an unprecedented protocol for radical cyclization of aldehydes with pendant alkenes via synergistic photoredox, cobaloxime, and amine catalysis. The transformation was achieved in the absence of external oxidants, providing a variety of 5-, 6-, and 7-membered ring products with alkene transposition in satisfactory yields. The reaction exhibits wide functional group compatibility and occurs under mild conditions with extrusion of H-2.

  DOI：

  10.1021/acs.orglett.0c02742

文献信息

• Fused imidazopyridine derivatives as antihyperlipidemic agents
  申请人：Takeda Chemical Industries, Ltd.

  公开号：US06235731B1

  公开（公告）日：2001-05-22

  A novel compound of the formula: wherein ring Q is an optionally substituted pyridine ring; One of R0, R1 and R2 is —Y0—Z0, and the other tow groups are a hydrogen, a halogen, an optionally substituted hydroxy group, a hydrocarbon group that may be an optionally substituted hydrocarbon group or an acyl group; Y0 is a bond or an optionally substituted bivalent hydrocarbon group; Z0 is a basic group which may be bonded via oxygen, nitrogen, —CO—, —CS—, —SO2N(R3)— (where R3 is hydrogen or an optionally substituted hydrocarbon group), or S(O)n (wherein n is to 0, 1 or 2); ......... is a single bond or a double bond, or a salt thereof, which has an excellent LDL receptor up-regulating, blood-lipids lowering, blood-sugar lowering and diabetic complication-ameliorating activity.

  其中环Q是一个可选择取代的吡啶环； R0、R1和R2中的一个是—Y0—Z0，另外两个基团是氢、卤素、可选择取代的羟基、可能是可选择取代的碳氢基团或酰基； Y0是一个键或一个可选择取代的二价碳氢基团； Z0是一种碱性基团，可以通过氧、氮、—CO—、—CS—、—SO2N(R3)—（其中R3是氢或可选择取代的碳氢基团）或S(O)n（其中n为0、1或2）与之键合； .........是一种单键或双键，或其盐，具有出色的LDL受体上调、降低血脂、降低血糖和改善糖尿病并发症的活性。
• New reactions of α-allylation of CH-acids with carbonyl groups
  作者：A. I. Moskalenko、V. I. Boev

  DOI：10.1134/s1070428015020049

  日期：2015.2

  New α-allylation reactions were performed of CH-acids with carbonyl groups (β-ketoacetic esters, phenylacetone, β-tetralone, ethyl acetate and its α-substituted derivatives) using as deprotonating reagents depending on the substrate acidity sodium hydride, potassium tert-butilate, and sodium bis(trimethylsilyl)-amide. BrCH2CH=CRR′ (R= R′ = H, Me; R = Me, R′ = CH2Ph, CH2CH2Ph) and BrCH2CH=X (X = cyclohexanylidene

  根据底物酸度，氢化钠，叔碳酸钾和苯甲酸的不同，使用带去质子试剂对具有羰基的CH-酸（β-酮乙酸酯，苯丙酮，β-四氢萘酮，乙酸乙酯及其α-取代衍生物）进行新的α-烯丙基化反应。丁酸酯和双（三甲基甲硅烷基）-酰胺钠。BrCH 2 CH = CRR'（R = R'= H，Me; R = Me，R'= CH 2 Ph，CH 2 CH 2 Ph）和BrCH 2 CH = X（X =环己叉基，4-吡喃基，4- N-Boc-哌啶亚基）用作烯丙基化剂。
• One Pot Synthesis of Spirocycles and Cyclopropa[<i>b</i>]pyrans by Alkenylation-Rearrangement of Cyclopropenes
  作者：Alejandro Puet、Eleonora Giona、Gema Domínguez、Javier Pérez-Castells

  DOI：10.1021/acs.joc.2c01420

  日期：2022.9.16

  achieved for spiro[2.4]heptanes if the cyclopropene is monosubstituted in C3. When an α,β-unsaturatedcarbonyl-containing bromide is used, an alternative cyclization takes place giving cyclopenta[c]cyclopropa[b]pyrans.

  一锅烯基化，然后是环丙烯的立体选择性 Alder-ene 环异构化，以高产率得到 (aza)spiro[2.4]庚烷和spiro[2.5]辛烷。如果环丙烯在 C3 中被单取代，则螺[2.4]庚烷可实现总反式非对映选择性。当使用含 α,β-不饱和羰基的溴化物时，会发生另一种环化反应，得到环戊二烯 [ c ] 环丙 [ b ] 吡喃。
• FUSED IMIDAZOPYRIDINE DERIVATIVES AS ANTIHYPERLIPIDEMIC AGENTS
  申请人：Takeda Chemical Industries, Ltd.

  公开号：EP0915888A1

  公开（公告）日：1999-05-19
• US6235731B1
  申请人：——

  公开号：US6235731B1

  公开（公告）日：2001-05-22