5,5-dimethyl-2-[4-(t-butoxycarbonylamino)phenyl]-1,3,2-dioxaborinane

• 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: 5,5-dimethyl-2-[4-(t-butoxycarbonylamino)phenyl]-1,3,2-dioxaborinane
• 英文别名: (4-((tert-butoxycarbonyl)amino)phenyl)boronic acid neopentylglycol ester；tert-butyl N-[4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyl]carbamate
• 化学式: C₁₆H₂₄BNO₄
• 分子量: 305.182
• InChiKey: CMIPZFPKDWQXNM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  56.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,5-dimethyl-2-[4-(t-butoxycarbonylamino)phenyl]-1,3,2-dioxaborinane 、 二氧化碳 在 [Rh(OH)(cod)]2 1,3-bis(di(4-methoxyphenyl)phosphino)propane 、 cesium fluoride 作用下， 以 1,4-二氧六环 为溶剂， 以88%的产率得到N-BOC-4-氨基苯甲酸
  参考文献：
  名称：

  Rhodium(I)-Catalyzed Carboxylation of Aryl- and Alkenylboronic Esters with CO₂

  摘要：

  When the esters of arylboronic acids with 2,2-dimethylpropan-1,3-diol were treated with a catalytic amount of [Rh(OH)(cod)]2 in the presence of 1,3-bis(diphenylphosphino)propane and CsF in dioxane at 60 degrees C under carbon dioxide atmosphere, the benzoic acid derivatives were obtained in good yields. Reactions of alkenylboronic esters also proceeded under similar conditions to give alpha,beta-unsaturated carboxylic acids. As these boronic esters are now easily available through coupling or direct borylation reactions, this method would be a useful method for the preparation of various functionalized aryl- and alkenyl-carboxylic acids.

  DOI：

  10.1021/ja061232m

文献信息

• Nickel-Catalyzed 1,2-Carboamination of Alkenyl Alcohols
  作者：Taeho Kang、Nana Kim、Peter T. Cheng、Hao Zhang、Klement Foo、Keary M. Engle

  DOI：10.1021/jacs.1c07112

  日期：2021.9.1

  An alcohol-directed, nickel-catalyzed three-component umpolung carboamination of unactivated alkenes with aryl/alkenylboronic esters and electrophilic aminating reagents is reported. This transformation is enabled by specifically tailored O-(2,6-dimethoxybenzoyl)hydroxylamine electrophiles that suppress competitive processes, including undesired β-hydride elimination and transesterification between

  报道了未活化烯烃与芳基/烯基硼酸酯和亲电子胺化试剂的醇导向、镍催化的三组分 umpolung 碳胺化反应。这种转化是通过专门定制的O -(2,6-二甲氧基苯甲酰基)羟胺亲电试剂实现的，该试剂抑制竞争过程，包括不需要的 β-氢化物消除和醇底物和亲电试剂之间的酯交换。该反应提供了所需的 1,2- 碳胺化产物，通常具有高区域和合成-非对映选择性，并表现出广泛的偶联伙伴和烯烃，包括复杂的天然产物。X 射线晶体学分析证实，各种机械实验和环状烯烃底物立体化学结果分析支持有机镍 (I) 物种的醇定向同步插入。
• Sulfonamide Directivity Enables Ni-Catalyzed 1,2-Diarylation of Diverse Alkenyl Amines
  作者：Omar Apolinar、Van T. Tran、Nana Kim、Michael A. Schmidt、Joseph Derosa、Keary M. Engle

  DOI：10.1021/acscatal.0c03857

  日期：2020.12.4

  amide-directed 1,2-diarylation, which involves carbonyl coordination. The synthetic utility of the method arises from the dual function of the sulfonamide as both a directing group and a masked amine nucleophile. This is highlighted by various product diversifications where complex amine compounds are synthesized in a two-step sequence of N-functionalization and deprotection of the sulfonyl group.

  据报道，在镍催化下，烯基磺酰胺与芳基碘化物和芳基硼​​酸酯的1，2-二芳基化。所开发的方法可以容忍具有不同电子特性和取代模式的偶联伙伴。全部容纳了二取代和三取代的烯烃以及远离该导向基团的烯烃。对照实验与该指导基团的N-Ni配位模式相一致，这与先前有关酰胺指导的1,2-二芳基化的报道相反，后者涉及羰基配位。该方法的合成用途源于磺酰胺既具有指导基团又具有掩蔽的胺亲核试剂的双重功能。各种产品多样化突显了这一点，其中复杂的胺化合物以两步的N顺序合成-官能化和磺酰基的脱保护。
• Electrophilic Sulfur Reagent Design Enables Directed <i>syn</i>-Carbosulfenylation of Unactivated Alkenes
  作者：Zi-Qi Li、Yilin Cao、Taeho Kang、Keary M. Engle

  DOI：10.1021/jacs.1c13252

  日期：2022.4.27

  A multi-component approach to structurally complex organosulfur products is described via the nickel-catalyzed 1,2-carbosulfenylation of unactivated alkenes with organoboron nucleophiles and tailored organosulfur electrophiles. The key to the development of this transformation is the identification of a modular N-alkyl-N-(arylsulfenyl)arenesulfonamide family of sulfur electrophiles. Tuning the electronic

  通过镍催化的未活化烯烃与有机硼亲核试剂和定制的有机硫亲电试剂的 1,2-羰基化，描述了一种结构复杂的有机硫产品的多组分方法。开发这种转化的关键是鉴定硫亲电子试剂的模块化N-烷基-N- (芳基亚磺基)芳基磺酰胺家族。通过计算研究检查，调整这些试剂中离去基团的电子和空间特性可控制途径选择性，有利于三组分偶联和抑制副反应。独特的syn-立体选择性不同于传统的涉及硫杂鎓离子中间体的亲电子硫基转移过程，它源于定向的芳基镍 (I) 迁移插入机制，正如通过反应动力学和对照实验所阐明的那样。一系列单齿、弱配位的天然导向基团（包括磺胺、醇、胺、酰胺和氮杂杂环）促进了反应性和区域选择性。
• Three-Component Asymmetric Ni-Catalyzed 1,2-Dicarbofunctionalization of Unactivated Alkenes via Stereoselective Migratory Insertion
  作者：Omar Apolinar、Taeho Kang、Turki M. Alturaifi、Pranali G. Bedekar、Camille Z. Rubel、Joseph Derosa、Brittany B. Sanchez、Quynh Nguyen Wong、Emily J. Sturgell、Jason S. Chen、Steven R. Wisniewski、Peng Liu、Keary M. Engle

  DOI：10.1021/jacs.2c06636

  日期：2022.10.26

  asymmetric 1,2-dicarbofunctionalization of unactivated alkenes with aryl iodides and aryl/alkenylboronic esters under nickel/bioxazoline catalysis is disclosed. A wide array of aryl and alkenyl nucleophiles are tolerated, furnishing the products in good yield and with high enantioselectivity. In addition to terminal alkenes, 1,2-disubstituted internal alkenes participate in the reaction, establishing two contiguous

  公开了在镍/生物恶唑啉催化下未活化烯烃与芳基碘化物和芳基/烯基硼酸酯的不对称 1,2-二碳官能化。可以耐受多种芳基和烯基亲核试剂，以良好的收率和高对映选择性提供产品。除了末端烯烃外，1,2-二取代的内部烯烃也参与反应，建立两个连续的立体中心，具有高非对映选择性和中等对映选择性。实验和计算技术的结合揭示了催化转化的机制，指向具有对映体决定迁移插入步骤的闭壳途径，
• Rhodium(I)-Catalyzed Carboxylation of Aryl- and Alkenylboronic Esters with CO₂
  作者：Kazutoshi Ukai、Masao Aoki、Jun Takaya、Nobuharu Iwasawa

  DOI：10.1021/ja061232m

  日期：2006.7.1

  When the esters of arylboronic acids with 2,2-dimethylpropan-1,3-diol were treated with a catalytic amount of [Rh(OH)(cod)]2 in the presence of 1,3-bis(diphenylphosphino)propane and CsF in dioxane at 60 degrees C under carbon dioxide atmosphere, the benzoic acid derivatives were obtained in good yields. Reactions of alkenylboronic esters also proceeded under similar conditions to give alpha,beta-unsaturated carboxylic acids. As these boronic esters are now easily available through coupling or direct borylation reactions, this method would be a useful method for the preparation of various functionalized aryl- and alkenyl-carboxylic acids.