Benzyl-diethylsilanyl-methyl-amine | 49543-88-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Benzyl-diethylsilanyl-methyl-amine
• 英文别名: N-diethylsilyl-N-methyl-1-phenylmethanamine
• CAS: 49543-88-6
• 化学式: C₁₂H₂₁NSi
• 分子量: 207.391
• InChiKey: XSKGVELGNTZWGK-UHFFFAOYSA-N

物化性质

• 沸点：
  259.7±19.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.88
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Benzyl-diethylsilanyl-methyl-amine 在 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 3,4,7,8-四甲基-1,10-菲罗啉 、 norbornene 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 以216 mg的产率得到C₁₂H₁₉NSi
  参考文献：
  名称：

  芳烃和苄型的C铱催化区域选择性硅烷化？仲胺指导的H键

  摘要：

  本文报道的是铱催化的苄胺芳族CH键和2 N-二烷基苯胺的苄基CH键的区域选择性甲硅烷基化反应。在该方法中，通过苄胺或苯胺与二乙基硅烷的脱氢偶联原位生成的（氢化）甲硅烷基胺在氨基的CH键γ处进行选择性甲硅烷基化。这种甲硅烷基化的产物适用于随后的氧化，卤化和交叉偶联反应，以递送苄胺和芳胺衍生物。

  DOI：

  10.1002/anie.201404620
• 作为产物：
  描述：

  N-甲基苯甲酰胺 在 chlorobis(cyclooctene)-iridium(I) dimer 、 二乙基硅烷 作用下， 反应 7.0h， 以98%的产率得到Benzyl-diethylsilanyl-methyl-amine
  参考文献：
  名称：

  Iridium-Catalyzed Reduction of Secondary Amides to Secondary Amines and Imines by Diethylsilane

  摘要：

  Catalytic reduction of secondary amides to imines and secondary amines has been achieved using readily available iridium catalysts such as [Ir(COE)(2)Cl](2) with diethylsilane as reductant. The stepwise reduction to secondary amine proceeds through an imine intermediate that can be isolated when only 2 equiv of silane is used. This system requires low catalyst loading and shows high efficiency (up to 1000 turnovers at room temperature with 99% conversion have been attained) and an appreciable level of functional group tolerance.

  DOI：

  10.1021/ja304547s

文献信息

• Seeking Heteroatom-Rich Compounds: Synthetic and Mechanistic Studies into Iron Catalyzed Dehydrocoupling of Silanes
  作者：Danila Gasperini、Andrew K. King、Nathan T. Coles、Mary F. Mahon、Ruth L. Webster

  DOI：10.1021/acscatal.0c01440

  日期：2020.6.5

  aminosilane synthesis along with kinetic studies using MeBnNH and MePhSiH2 as coupling partners. The kinetic studies suggest a reversible reaction with silane which generates aminosilane and an Fe-hydride dimer that undergoes rate-limiting protonolysis with amine with N–H bond cleavage in the transition state, consistent with a primary KIE of 2.42(3). The presence of dimers as on-cycle intermediates was analyzed

  提出了使用铁预催化剂（1）对硅烷与胺，膦和醇进行脱氢偶联的详细合成研究。我们提供了30多个氨基硅烷合成实例，以及使用MeBnNH和MePhSiH 2进行的动力学研究作为耦合伙伴。动力学研究表明与硅烷发生可逆反应，生成氨基硅烷，然后生成Fe-氢化物二聚体，该二聚体与胺进行限速质子分解，在过渡态下具有NH键断裂，与初始KIE为2.42（3）一致。深入分析了二聚体作为循环中间体的存在。除此之外，我们还研究了膦基硅烷形成的底物范围，该范围显示了优先的杂脱氢偶联，使膦基硅烷与伯硅烷和仲硅烷一起生成。也可以制备甲硅烷基醚，并且含有烯烃官能度的醇不显示任何还原双键的趋势。
• Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations
  申请人：The University of Chicago

  公开号：US10647733B2

  公开（公告）日：2020-05-12

  Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

  基于以氮为供体的有机桥联配体，包括基于1,3-二酮亚胺（NacNac）、联吡啶和柳酸亚胺的金属-有机框架（MOFs）组成物被合成，然后用金属前驱体如第一行过渡金属的络合物进行后合成金属化。有机桥联配体的金属络合物也可以直接并入MOFs中。MOFs提供了一个多功能的、可回收和可重复使用的单点固体催化剂家族，用于催化各种不对称有机转化。这些固体催化剂也可以集成到流动反应器或超临界流体反应器中。
• Preparation Of Aromatic-Substituted Silylamines By The Dehydrogenative Coupling Of Aromatic-Substituted Amine N-H And Si-H Bonds
  申请人：California Institute Of Technology

  公开号：US20190218232A1

  公开（公告）日：2019-07-18

  The present disclosure is directed at methods of forming an N—Si silyl bond, the method comprising contacting an organic substrate comprising an aromatic amine having at least one N—H bond with a mixture comprising of (a) at least one hydrosilane or hydrosiloxane and (b) at least one hydroxide or alkoxide, under conditions sufficient to form the N—Si bond. The disclosure is further directed to the compositions involved in these methods and the products that result therefrom.

  本公开涉及形成N-Si硅基键的方法，所述方法包括将含有至少一个N-H键的芳香胺的有机基质与包括（a）至少一种氢硅烷或氢硅氧烷以及（b）至少一种氢氧化物或烷氧化物的混合物接触，在足以形成N-Si键的条件下进行。该公开进一步涉及参与这些方法的组合物以及由此产生的产品。
• Bipyridine- and Phenanthroline-Based Metal–Organic Frameworks for Highly Efficient and Tandem Catalytic Organic Transformations via Directed C–H Activation
  作者：Kuntal Manna、Teng Zhang、Francis X. Greene、Wenbin Lin

  DOI：10.1021/ja512478y

  日期：2015.2.25

  We report here the synthesis of a series of robust and porous bipyridyl- and phenanthryl-based metal-organic frameworks (MOFs) of UiO topology (BPV-MOF, mBPV-MOF, and mPT-MOF) and their postsynthetic metalation to afford highly active single-site solid catalysts. While BPV-MOF was constructed from only bipyridyl-functionalized dicarboxylate linker, both mBPV- and mPT-MOF were built with a mixture of bipyridyl- or phenanthryl-functionalized and unfunctionalized dicarboxylate linkers. The postsynthetic metalation of these MOFs with [Ir(COD)(OMe)]2 provided Ir-functionalized MOFs (BPV-MOF-Ir, mBPV-MOF-Ir, and mPT-MOF-Ir), which are highly active catalysts for tandem hydrosilylation of aryl ketones and aldehydes followed by dehydrogenative ortho-silylation of benzylicsilyl ethers as well as C-H borylation of arenes using B2pin2. Both mBPV-MOF-Ir and mPT-MOF-Ir catalysts displayed superior activities compared to BPV-MOF-Ir due to the presence of larger open channels in the mixed-linker MOFs. Impressively, mBPV-MOF-Ir exhibited high TONs of up to 17000 for C-H borylation reactions and was recycled more than 15 times. The mPT-MOF-Ir system is also active in catalyzing tandem dehydrosilylation/dehydrogenative cyclization of N-methylbenzyl amines to azasilolanes in the absence of a hydrogen acceptor. Importantly, MOF-Ir catalysts are significantly more active (up to 95 times) and stable than their homogeneous counterparts for all three reactions, strongly supporting the beneficial effects of active site isolation within MOFs. This work illustrates the ability to increase MOF open channel sizes by using the mixed linker approach and shows the enormous potential of developing highly active and robust single-site solid catalysts based on MOFs containing nitrogen-donor ligands for important organic transformations.
• A novel method for the reduction of schiff bases using catalytic hydrosilylation
  作者：Iwao Ojima、Tetsuo Kogure、Yoichiro Nagai

  DOI：10.1016/s0040-4039(01)96182-9

  日期：1973.1