2-甲基-2-丙基3-丁烯-2-基氨基甲酸酯 | 267668-37-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 2-甲基-2-丙基3-丁烯-2-基氨基甲酸酯
• 英文名称: tert-butyl (but-3-en-2-yl)carbamate
• 英文别名: N-Boc-(+/-)-3-aminobutene；tert-butyl N-but-3-en-2-ylcarbamate
• CAS: 267668-37-1
• 化学式: C₉H₁₇NO₂
• 分子量: 171.239
• InChiKey: KIFRIUDSLUQLOC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-甲基-2-丙基3-丁烯-2-基氨基甲酸酯 在 2,2'-联吡啶 、 copper(l) chloride 正丁基锂 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 (4S,5S)-3,3-Dichloro-4-chloromethyl-5-methyl-2-oxo-pyrrolidine-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Transition metal-catalyzed radical cyclizations: a low-temperature process for the cyclization of N-protected N-allyltrichloroacetamides to trichlorinated .gamma.-lactams and application to the stereoselective preparation of .beta.,.gamma.-disubstituted .gamma.-lactams

  摘要：

  Cyclizations of N-substituted N-allyltrichloroacetamides, where the substituent is an alkyl, Cbz, Boc, Ts, or Ms group, are catalyzed by a 1:1 mixture of CuCl and bipyridine to give the corresponding beta,gamma-trichlorinated gamma-lactams in high yields. The reactions proceed at temperatures from -78-degrees-C to room temperature. Cyclizations of N-allyltrichloroacetamides of acyclic secondary allylic amines are achieved with good selectivity; the cis/trans ratios of the gamma-lactams formed were dependent on the substituents on the nitrogen atom. The stereochemical outcome is compared with that of free-radical cyclization.

  DOI：

  10.1021/jo00054a034
• 作为产物：
  描述：

  N-重氮基氨基甲酸叔-丁基酯 在 偶氮二异丁腈 、 三正丁基氢锡 、 iron(II) chloride 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 1.0h， 生成 2-甲基-2-丙基3-丁烯-2-基氨基甲酸酯
  参考文献：
  名称：

  Fe(II)-Catalyzed Imidation of Allyl Sulfides and Subsequent [2,3]-Sigmatropic Rearrangement. Preparation of α-Branched N-tert-Butyloxycarbonyl (Boc)-Protected N-Allylamines

  摘要：

  Allyl aryl sulfides 1 and 5 were shown to undergo an imidation/[2,3]-sigmatropic rearrangement reaction upon treatment with N-tert-butyloxycarbonyl azide (BocN(3)) and catalytic amounts of FeCl2 in CH2Cl2. The N-Boc-protected N-allyl sulfenamides 3 and 21 were obtained in yields between 48 and 75% (12 examples), Whereas the reaction is well suited for the transformation of alpha-unbranched sulfides to a-branched sulfenamides, the enantiomerically pure alpha-branched sulfides 10 and 13 reacted sluggishly. The corresponding sulfenamides 22 and 23 were obtained in only moderate enantiomeric excess (36-39% eel. A reaction mechanism is proposed that postulates the intermediacy of an N-Boc-substituted Fe(IV)-nitrene complex 14 acting as the imidation reagent in the catalytic cycle. Possible side reactions are discussed. The benzenesulfenamides 3 were further converted into N-Boc-N-allylamines 4 by removal of the phenylsulfanyl group. Bu3SnH in benzene was found to be the reagent of choice for the deprotection of alpha-branched amines that bear a secondary allyl substituent (five examples, 71-93% yield). This method failed for the alpha-branched amines 3i-k with a tertiary allyl substituent. The phenylsulfanyl group was finally removed with P(OEt)(3)/NEt3 in CH2Cl2 (three examples, 43-62% yield).

  DOI：

  10.1021/jo991569p

文献信息

• [EN] MACROCYCLIC SPIROETHERS AS MCL-1 INHIBITORS<br/>[FR] SPIROÉTHERS MACROCYCLIQUES UTILISÉS EN TANT QU'INHIBITEURS DE MCL-1
  申请人：ASCENTAGE PHARMA SUZHOU CO LTD

  公开号：WO2020147802A1

  公开（公告）日：2020-07-23

  Provided are compounds represented by Formula (I-A) and the pharmaceutically acceptable salts and solvates thereof, wherein R8, R9a, R9b, R9c, R9d, X, Y, Z, Z1, W, and (aa) are as defined as set forth in the specification. Provided are also compounds of Formula (I-A) for use to treat a condition or disorder responsive to Mcl-1 inhibition such as cancer.

  提供的是由公式（I-A）表示的化合物以及其中所述的药物可接受的盐和溶剂化物，其中R8，R9a，R9b，R9c，R9d，X，Y，Z，Z1，W和（aa）如说明书所述定义。还提供了用于治疗对Mcl-1抑制有反应的条件或疾病的公式（I-A）化合物，例如癌症。
• Direct Synthesis of Highly Substituted Pyrroles and Dihydropyrroles Using Linear Selective Hydroacylation Reactions
  作者：Manjeet K. Majhail、Paul M. Ylioja、Michael C. Willis

  DOI：10.1002/chem.201600311

  日期：2016.6.1

  diphosphine ligands, such as (Cy2 P)2 NMe or bis(diphenylphosphino)methane (dppm), are effective at catalysing the union of aldehydes and propargylic amines to deliver the linear hydroacylation adducts in good yields and with high selectivities. In situ treatment of the hydroacylation adducts with p-TSA triggers a dehydrative cyclisation to provide the corresponding pyrroles. The use of allylic amines, in place

  含有小咬角二膦配体（例如 (Cy2 P)2 NMe 或双(二苯基膦)甲烷 (dppm)）的铑 (I) 催化剂可有效催化醛和炔丙胺的结合，以良好的方式生成线性加氢酰化加合物。产率和高选择性。用 p-TSA 对加氢酰化加合物进行原位处理会引发脱水环化，从而提供相应的吡咯。使用烯丙胺代替炔丙底物可产生官能化的二氢吡咯。加氢酰化反应也可以在级联过程中与使用芳基硼酸的Rh(I)催化的Suzuki型偶联结合起来，提供高度取代的吡咯的三组分组装体。
• <i>N</i>-Methyl Allylic Amines from Allylic Alcohols by Mitsunobu Substitution Using <i>N</i>-Boc Ethyl Oxamate
  作者：Branca C. van Veen、Steven M. Wales、Jonathan Clayden

  DOI：10.1021/acs.joc.1c00918

  日期：2021.6.18

  synthesis of a range of N-methyl allylic amines. Primary and secondary allylic alcohols underwent a regioselective Mitsunobu reaction with readily accessible N-Boc ethyl oxamate to deliver the corresponding N-Boc allylic amines, including in enantiopure form via stereospecific substitution. Subsequent N-methylation and Boc deprotection without chromatography yielded the amine products as hydrochloride salts

  我们报告了一系列N-甲基烯丙胺的实用、可扩展合成。伯烯和仲烯丙醇与容易获得的N- Boc 草酸乙酯进行区域选择性的 Mitsunobu 反应，以提供相应的N- Boc 烯丙胺，包括通过立体特异性取代的对映纯形式。随后的N-甲基化和 Boc 脱保护无需色谱法得到胺产物，为盐酸盐。该方法解决了将市售醇转化为通常具有挥发性的N-甲基烯丙胺的问题，其中许多具有有限的商业可用性。
• Novel Bicyclic Sulfonamides for Use as Glucocorticoid Receptor Modulators in the Treatment of Inflammatory Diseases
  申请人：Bladh Hakan

  公开号：US20090124607A1

  公开（公告）日：2009-05-14

  Compounds of formula (I): or a pharmaceutically acceptable salt thereof; compositions comprising them, processes for preparing them and their use in medical therapy (for example modulating the glucocorticoid receptor in a warm blooded animal).

  式(I)的化合物或其药学上可接受的盐；包含它们的组合物、制备它们的过程以及它们在医疗治疗中的用途（例如在温血动物中调节糖皮质激素受体）。
• Macrocyclic Tertiary Amine Beta-Secretase Inhibitors for the Treatment of Alzheimer's Disease
  申请人：Nantermet Philippe G.

  公开号：US20080269302A1

  公开（公告）日：2008-10-30

  The present invention is directed to macrocyclic tertiary amine compounds represented by general formula (I) which are inhibitors of the beta-secretase enzyme and that are useful in the treatment of diseases in which the beta-secretase enzyme is involved, such as Alzheimer's disease. The invention is also directed to pharmaceutical compositions comprising these compounds and the use of these compounds and compositions in the treatment of such diseases in which the beta-secretase enzyme is involved.

  本发明涉及由通式(I)表示的大环三级胺化合物，它们是β-分泌酶酶的抑制剂，并且在治疗β-分泌酶酶参与的疾病，如阿尔茨海默病方面具有用途。本发明还涉及包含这些化合物的制药组合物，以及在治疗β-分泌酶酶参与的这些疾病方面使用这些化合物和组合物。