(3R,4R)-3-(4-bromophenyl)-4,6-diphenyl-1-tosyl-3,4-dihydropyridin-2(1H)-one | 1380402-52-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (3R,4R)-3-(4-bromophenyl)-4,6-diphenyl-1-tosyl-3,4-dihydropyridin-2(1H)-one
• 英文别名: (3R,4R)-3-(4-bromophenyl)-1-(4-methylphenyl)sulfonyl-4,6-diphenyl-3,4-dihydropyridin-2-one
• CAS: 1380402-52-7
• 化学式: C₃₀H₂₄BrNO₃S
• 分子量: 558.495
• InChiKey: QNJMPVAEEIYFQJ-YTMVLYRLSA-N

物化性质

• 熔点：
  210-214 °C
• 沸点：
  666.3±65.0 °C(Predicted)
• 密度：
  1.404±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  36
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  62.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  对溴苯乙酸 在 (+)-苯并四咪唑 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 2.33h， 生成 (3R,4R)-3-(4-bromophenyl)-4,6-diphenyl-1-tosyl-3,4-dihydropyridin-2(1H)-one 、 3-(4-bromophenyl)-4,6-diphenyl-1-tosyl-3,4-dihydropyridin-2(1H)-one
  参考文献：
  名称：

  二氢吡啶酮：催化不对称合成，N到C磺酰基转移和衍生化

  摘要：

  苯并四咪唑（1）促进了从芳酸中衍生出来的烯醇铵盐与N-甲苯磺酰基-α，β-不饱和酮亚胺的反应，从而使二氢吡啶酮具有非对映异构和对映异构控制性（见方案）。这些产品容易进行N-至C-磺酰基的光异构化，并衍生化得到立体定义的哌啶和四氢吡喃。

  DOI：

  10.1002/anie.201109061

文献信息

• An Upstream By-product from Ester Activation via NHC-Catalysis Catalyzes Downstream Sulfonyl Migration Reaction
  作者：Runfeng Han、Liwenze He、Lin Liu、Xingang Xie、Xuegong She

  DOI：10.1002/asia.201500959

  日期：2016.1

  A sequential reaction combining N‐heterocyclic carbene (NHC) and N‐hydroxyphthalimide (NHPI) catalysis allowed for the upstream by‐product NHPI, which was generated in the NHC‐catalyzed cycloaddition reaction, to act as the catalyst for a downstream nitrogen‐to‐carbon sulfonyl migration reaction. Enantiomeric excess of the major product in the cycloaddition reaction remained intact in the follow‐up

  N-杂环卡宾（NHC）和N-羟基邻苯二甲酰亚胺（NHPI）催化相结合的顺序反应允许上游副产物NHPI在NHC催化的环加成反应中生成，充当下游氮到氮的催化剂碳磺酰基迁移反应。在后续的磺酰基迁移反应中，环加成反应中主要产物的对映体过量保持完整。
• A Recyclable, Immobilized Analogue of Benzotetramisole for Catalytic Enantioselective Domino Michael Addition/Cyclization Reactions in Batch and Flow
  作者：Javier Izquierdo、Miquel A. Pericàs

  DOI：10.1021/acscatal.5b02121

  日期：2016.1.4

  A polystyrene-supported, enantiopure benzote-tramisole (BTM) analogue (5) has been synthesized from (2S,3S)-phenylglycidol through a five-step sequence involving a copper-catalyzed alkyne azide cycloaddition (CuAAC) reaction as the final, immobilization step. The functional resin 5 (f = 0.9 mmol g(-1)) has been successfully used as a highly active and enantioselective catalyst in the domino Michael addition/cyclization reaction of in situ activated arylacetic acids (7) with chalcone-type tosylimines (6), leading to dihydropyridinones 8 (17 examples) to afford the products with excellent yields and very high enantioselectivity (mean ee 97.4%). The deactivation of 5 by species present during the catalytic process has been studied, and pivaloyl chloride (required for the activation of the arylacetic acid) has been identified as the main source of deactivation. A simple experimental protocol taking this fact into account has allowed the multiple recycling of 5 with only a marginal decrease in catalytic activity and the implementation of a continuous flow process where the activation of phenylacetic acid (residence time 14.2 min), the asymmetric domino Michael addition/cydization reaction (residence time 7.5 min), and aqueous workup are performed sequentially, delivering the dihydropyridinone product as a clean dichloromethane solution (0.54 mmol catalyst sample; 11 h operation; 8a (4.44 g, >99.9% ee)). The supported catalyst 5 has also been used in a new domino Michael addition/cydization reaction involving saccharin-derived tosylimines 9 as electrophiles, leading to 8,9-dihydro-7H-benzo[4,5]isothiazolo [2,3-[a]pyridin-7-one 5,5-dioxides 10 (8 examples) in high isolated yields and diastereoselectivities and excellent enantioselectivities (mean ee 98%). A single sample of 5 (0.5 g, 0.45 mmol) has been used for the sequential preparation in batch of a library of 7 different derivatives 10 at the gram scale (ca. 10 g, accumulated TON = 51), the whole process being performed without any column chromatographic purification. The increased diastereoselectivity recorded with 5 in reactions involving sterically congested arylacetic acids (with respect to homogeneous BTM) has been rationalized through the occurrence of steric interactions between the sulfonylimine and the linker plus support catalyst fragments leading to additional destabilization of the transition state leading to the minor, cis diastereomer of products 8/10.
• Dihydropyridones: Catalytic Asymmetric Synthesis, N- to C-Sulfonyl Transfer, and Derivatizations
  作者：Carmen Simal、Tomas Lebl、Alexandra M. Z. Slawin、Andrew D. Smith

  DOI：10.1002/anie.201109061

  日期：2012.4.10

  promotes the reaction of ammonium enolates derived from arylacetic acids with N‐tosyl‐α,β‐unsaturated ketimines, thus giving dihydropyridones with high diastereo‐ and enantiocontrol (see scheme). These products readily undergo N‐ to C‐sulfonyl photoisomerization and are derivatized to afford stereodefined piperidines and tetrahydropyrans.

  苯并四咪唑（1）促进了从芳酸中衍生出来的烯醇铵盐与N-甲苯磺酰基-α，β-不饱和酮亚胺的反应，从而使二氢吡啶酮具有非对映异构和对映异构控制性（见方案）。这些产品容易进行N-至C-磺酰基的光异构化，并衍生化得到立体定义的哌啶和四氢吡喃。