3-Bromo-2-(tert-butylsulfonyl)-1-propene | 97147-24-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 磺酰类
• 英文名称: 3-Bromo-2-(tert-butylsulfonyl)-1-propene
• 英文别名: 3-bromo-2-(tert-butylsulfonyl)-propene；3-bromo-2-t-butylsulfonyl-1-propene；1-Propene, 3-bromo-2-[(1,1-dimethylethyl)sulfonyl]-；2-(3-bromoprop-1-en-2-ylsulfonyl)-2-methylpropane
• CAS: 97147-24-5
• 化学式: C₇H₁₃BrO₂S
• 分子量: 241.149
• InChiKey: RHICPTUSXIFNEF-UHFFFAOYSA-N

物化性质

• 熔点：
  43 °C
• 沸点：
  326.3±25.0 °C(Predicted)
• 密度：
  1.391±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-Bromo-2-(tert-butylsulfonyl)-1-propene 在 碳酸氢钠 、 三氟乙酸 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 4.5h， 生成 2-(t-Butylsulfonyl)-2-propenyloxycarbonyl-L-phenylalanine
  参考文献：
  名称：

  Amino-Protecting Groups Subject to Deblocking under Conditions of Nucleophilic Addition to a Michael Acceptor. Structure−Reactivity Studies and Use of the 2-(tert-Butylsulfonyl)-2-propenyloxycarbonyl (Bspoc) Group

  摘要：

  A new type of amino-protecting group is described in which a Michael acceptor is incorporated into the protectant so that treatment with a nucleophile will trigger deblocking. Comparison of various Michael accepters showed that for several key electron-withdrawing groups, the order of reactivity was C6H5SO2 > Me3CSO2 > COOEt > CsH5SO > C(6)H(4)NO(2-)p. The reactivity of the nucleophile. (e.g., primary and secondary aliphatic amines) followed an order related to both intrinsic basicity and steric effects. beta-Substituents in the Michael acceptor caused significant retardation of the deblocking process. The Bspoc function was chosen for initial elaboration into a practical system for use in peptide synthesis. Bspoc amino acid chlorides were used as coupling agents and silica-tethered secondary amines as deblocking agents. With the latter, deblocking occurs cleanly and no byproducts remain in the organic solvent in which the deblocking is executed.

  DOI：

  10.1021/jo982141d
• 作为产物：
  描述：

  1,3-Dibromo-2-tert-butylsulfanyl-propane 在 sodium acetate 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 四氯化碳 、 二氯甲烷 为溶剂， 反应 5.75h， 生成 3-Bromo-2-(tert-butylsulfonyl)-1-propene
  参考文献：
  名称：

  3-溴-2-叔丁基磺酰基-1-丙烯。通用的多偶联试剂第1部分

  摘要：

  由烯丙基叔丁基硫醚分两步制备3-溴-2-叔丁基磺酰基-1-丙烯，总产率为70％。该试剂可与多种亲核试剂（胺，硫醇盐，锂和酮烯酸酯，镁，锌和锂有机金属化合物）选择性反应，以典型的80-90％的产率提供类型的不饱和砜。砜还可以在锌的存在下与各种亲电试剂（醛，酮，腈和亚胺）反应，以高收率提供官能化的不饱和砜类型。

  DOI：

  10.1016/s0040-4020(01)86151-2

文献信息

• Reagents for rapid peptide synthesis
  申请人：Research Corporation Technologies, Inc.

  公开号：US05221754A1

  公开（公告）日：1993-06-22

  This invention relates to compounds of the formula: ##STR1## wherein R is an electron withdrawing group; R.sub.1 is H or COZ; X.sub.1 and X.sub.2 are independently H, lower alkyl, aryl, aryl lower-alkyl or polystyrene or R and X.sub.1 taken together with the carbon atoms to which they are attached form a ring containing from 4 to 15 ring carbon atoms and may contain up to 2 heteroatoms, wherein the heteroatoms are O, S, or N; and Z is an amino acid residue, a peptide residue or a leaving group. The compounds of the present invention are adaptable as blocking or protecting groups for an amine composition useful in peptide synthesis. The present invention is also directed to a method of protecting an amino group of an organic molecule during a reaction which modifies a portion of the molecule other than the protected amino group.

  本发明涉及以下结构的化合物：##STR1## 其中R是一个电子吸引基团；R.sub.1是H或COZ；X.sub.1和X.sub.2独立地是H、较低的烷基、芳基、芳基较低烷基或聚苯乙烯，或者R和X.sub.1与它们附着的碳原子一起形成一个含有4到15个环碳原子并且可能含有最多2个杂原子的环，其中杂原子是O、S或N；Z是氨基酸残基、肽残基或离去基团。本发明的化合物可用作肽合成中有用的胺组成部分的阻断或保护基团。本发明还涉及在修改分子的除受保护的氨基团之外的部分时保护有机分子的氨基团的方法。
• Synthesis and use of amino acid fluorides as peptide coupling reagents
  申请人：Research Corporation Technologies, Inc.

  公开号：US05360928A1

  公开（公告）日：1994-11-01

  A compound of the formula ##STR1## or the acid fluoride salts thereof wherein BLK is an N-amino protecting group or hydrogen AA is an amino acid residue and X is H or a protecting group useful as a coupling agent in peptide synthesis.

  化合物的公式为##STR1##或其酸氟化物盐，在其中BLK是N-氨基保护基或氢，AA是氨基酸残基，X是H或作为肽合成中偶联剂有用的保护基。
• Preparation and Reactivity of Polyfunctional Zinc and Copper Organometallics Bearing Sulfur Functionalities
  作者：S. Achyutha Rao、Tso-Sheng Chou、Ioana Schipor、Paul Knochel

  DOI：10.1016/s0040-4020(01)88872-4

  日期：1992.1

  phenyl sulfides 6 were found to insert zinc dust in THF under very mild conditions (10–25 °C, 0.5–2 h) leading to zinc α-thioorganometallics. After a transmetallation with CuCN·2 LiCl, the corresponding copper reagents 8 and 7 reacted with various electrophiles (1-haloalkynes, aldehydes, enones, acyl chlorides, allylic halides, trialkyltin halides) affording polyfunctional thioesters and sulfides of type

  Iodomethylthiobenzoate 5和α-氯代苯基硫化物6被发现非常温和的条件（10-25℃，0.5-2 1H）导致锌α-thioorganometallics下插入在THF锌粉。用CuCN·2 LiCl进行金属转移后，相应的铜试剂8和7与各种亲电试剂（1-卤代炔烃，醛，烯酮，酰氯，烯丙基卤化物，三烷基卤化锡）反应，得到9或10型多官能硫酯和硫化物。高产。特别令人感兴趣的是，与α-硫代碳酸锂相反，这些锌铜试剂可以带有各种官能团，例如酯或腈。相同的方法使各种γ硫代取代的锌和铜的试剂轴承苯硫基，苯基亚磺酰基，或α-（苯基磺酰基）乙烯基官能度（制备20-22），这也显示了良好的能力以形成新carboncarbon键。
• 5-Endo-Trigonal ring closures of unsaturated sulfones.
  作者：P. Auvray、P. Knochel、J.F. Normant

  DOI：10.1016/s0040-4039(00)88929-7

  日期：1985.1

  The γ -functionalized unsaturated sulfones 5a-5d, 8, 11 and 15 respectively cyclize to the 5-membered heterocycles 6a-6d, 9, 14 and to the 5-membered carbocycle 16 in good yields. These ring closures are all 5-Endo-Trig processes.

  γ-官能化的不饱和砜5a-5d，8、11和15分别以良好的产率环化成5元杂环6a-6d，9、14和5元碳环16。这些闭环都是5-Endo-Trig过程。
• Highly Stereoselective <i>C</i>-Allylation of an Enantiopure α-Sulfinyl Thioacetamide
  作者：Stéphanie Nowaczyk、Carole Alayrac、Patrick Metzner、Marie-Thérèse Averbuch-Pouchot

  DOI：10.1021/jo0258610

  日期：2002.9.1

  The alkylation of the lithium enolate of enantiopure alpha-cyclohexylsulfinyl thioacetamide 1 with allyl bromides 5 possessing an electron-withdrawing group at the vinylic position does not occur at the sulfur center - as expected in the sulfur series - but at the carbon center through conjugate addition followed by bromide elimination. The modest to excellent 1,2-asymmetric induction achieved by the alkylsulfinyl group (dr up to 100:0) is explained by an electronic model.