di-tert-butyl α-diazomethylphosphonate | 1367878-23-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: di-tert-butyl α-diazomethylphosphonate
• 英文别名: di-tert-butyl diazomethylphosphonate；2-[Diazomethyl-[(2-methylpropan-2-yl)oxy]phosphoryl]oxy-2-methylpropane
• CAS: 1367878-23-6
• 化学式: C₉H₁₉N₂O₃P
• 分子量: 234.235
• InChiKey: XDGOZIGBDIDWBE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  37.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  di-tert-butyl α-diazomethylphosphonate 在 sodium tetrahydroborate 、 samarium diiodide 、 三丁基膦 、 (2S,4S,5R)-1-(3,5-di-tert-butyl-2,6-diethoxybenzyl)-2-((R)-hydroxy(6-(naphthalene-2-yl)quinolin-4-yl)methyl)-5-vinylquinuclidin-1-ium chloride 、 caesium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 11.0h， 生成 di-tert-butyl ((1S, 2R)-1-amino-2-(2-bromophenyl)-2-(3, 5-di-tert-butyl-4-hydroxyphenyl)ethyl)phosphonate
  参考文献：
  名称：

  Enantioselective 1,6‐Conjugate Addition of Dialkyl α‐Diazo Methylphosphonate to para ‐Quinone Methides

  摘要：

  AbstractAn asymmetric 1,6‐conjugate addition reaction of dialkyl diazomethylphosphonates to para‐quinone methides promoted by phase‐transfer catalysis has been developed. A series of chiral diarylmethylated diazomethylphosphonates were accessed with up to 85% yields and 99% ee enantioselectivities. The resulting products were further transformed into bioactive compounds, namely, a chiral dihydrocinnoline phosphonate and a chiral α‐aminophosphonate, bearing diarylmethine stereogenic centers.magnified image

  DOI：

  10.1002/adsc.202100881
• 作为产物：
  描述：

  O-dibenzyl-aminomethylphosphonate 在 溶剂黄146 、 sodium nitrite 、 碳酸氢钠 作用下， 以 水 、 二氯甲烷 为溶剂， 反应 0.17h， 生成 di-tert-butyl α-diazomethylphosphonate
  参考文献：
  名称：

  手性布朗斯台德酸催化α-重氮二烷基膦酸二烷基酯与N-氨基甲酰基亚胺的高效不对称曼尼希反应

  摘要：

  开发了一种有效的方法，该方法涉及在二烷基重氮甲基膦酸酯和N-氨基甲酰基亚胺的不对称曼尼希反应中首先使用手性磷酸作为催化剂。仅使用0.1 mol％的催化剂1f，反应平稳进行，并以高达97％的收率和> 99％ee的产率生产相应的β-氨基-α-重氮膦酸酯。

  DOI：

  10.1021/ol300664d

文献信息

• Asymmetric acyl-Mannich reaction of isoquinolines with α-(diazomethyl)phosphonate and diazoacetate catalyzed by chiral Brønsted acids
  作者：Wei Wu、Yan Wang、Jing Guo、Liu Cai、Yuan Chen、Yanmin Huang、Yungui Peng

  DOI：10.1039/d0cc03201h

  日期：——

  An efficient asymmetric acyl-Mannich reaction of isoquinolines with α-(diazomethyl)phosphonate and diazoacetate has been developed using chiral spiro phosphoric acids as catalysts. This reaction allowed the construction of a series of chiral 1,2-dihydroisoquinolines bearing a tertiary stereocenter at the C1 position with up to 98% yield and 99% ee.

  使用手性螺环磷酸作为催化剂，已经开发了异喹啉与α-（重氮甲基）膦酸酯和重氮乙酸酯的有效不对称酰基曼尼希反应。该反应允许构建一系列手性的1,2-二氢异喹啉，在C1位置带有叔立体中心，产率高达98％，ee高达99％。
• Catalytic Asymmetric (3 + 3) Cycloaddition of Oxyallyl Zwitterions with α-Diazomethylphosphonates
  作者：Yan Liu、Xian Peng、Rui She、Xin Zhou、Yungui Peng

  DOI：10.1021/acs.orglett.1c02809

  日期：2021.9.17

  The unique structure of oxyallyls represents a significant challenge for their catalytic asymmetric applications. Herein, an unprecedented chiral imidodiphosphoric acid-catalytic enantioselective (3 + 3) cycloaddition between oxyallyl zwitterions generated in situ from α-haloketones and α-diazomethylphosphonates was developed. Pharmaceutically interesting chiral pyridazine-4(1H)-ones were obtained

  氧烯丙基的独特结构对其催化不对称应用提出了重大挑战。在此，开发了一种前所未有的手性亚氨基二磷酸催化的对映选择性（3 + 3）环加成反应，在由 α-卤代酮和 α-重氮甲基膦酸酯原位生成的氧烯丙基两性离子之间进行了环加成反应。药学上令人感兴趣的手性哒嗪-4( 1H )-酮以高达 98% 的收率获得，具有出色的立体选择性（高达 99% ee，> 99:1 dr）。
• Catalytic Asymmetric Tandem Reaction of <i>o</i>-Alkynylbenzaldehydes, Amines, and Diazo Compounds
  作者：Wei Wu、Na Liao、Qi Wei、Jiaying Huang、Qi Huang、Yungui Peng

  DOI：10.1021/acs.orglett.1c02433

  日期：2021.9.3

  An efficient asymmetric tandem reaction of o-alkynylbenzaldehydes, amines, and diazo compounds catalyzed by chiral silver imidodiphosphate has been established. Chiral 1,2-dihydroisoquinoline analogues have a tertiary stereocenter at the C1 position, and substituents at the C3 position are available with up to 97% yields and 98% ee. These products can be elaborated into the corresponding β-aminophosphonates

  已经建立了由手性亚氨基二磷酸银催化的邻炔基苯甲醛、胺和重氮化合物的有效不对称串联反应。手性 1,2-二氢异喹啉类似物在 C1 位有一个叔立构中心，C3 位有取代基，产率高达 97%，ee 高达 98%。这些产品可以加工成相应的 β-氨基膦酸盐或 PARP1 抑制剂类似物。
• Asymmetric Reaction of α-Diazomethylphosphonates with α-Ketoesters To Access Optically Active α-Diazo-β-hydroxyphosphonate Derivatives
  作者：Fei Du、Jiao Zhou、Yungui Peng

  DOI：10.1021/acs.orglett.7b00128

  日期：2017.3.17

  The first example for asymmetric reaction of diazomethylphosphonates with α-ketoesters was realized in the catalysis of hydroquinidine-derived bifunctional thiourea. A methodology was established to access a series of chiral α-diazo-β-hydroxyphosphonate derivatives containing various functional groups with high enantioselectivities and yields. The resulting products could be further transformed into

  重氮基甲基膦酸酯与α-酮酸酯不对称反应的第一个实例是在对苯二酚衍生的双官能硫脲的催化中实现的。建立了一种方法，以获取一系列具有高对映选择性和高收率的，包含各种官能团的手性α-重氮-β-羟基膦酸酯衍生物。所得产物可进一步转化为手性叔β-羟基膦酸酯和α-卤代磷霉素衍生物，尤其是α-氟化物类似物。
• Asymmetric Addition of α-Diazomethylphosphonate to Alkylideneindolenine Catalyzed by a Trifunctional BINAP-Based Monophosphonium Salt
  作者：Peng Zhu、Yi Yang、Yan Liu、Yungui Peng

  DOI：10.1021/acs.orglett.2c00213

  日期：2022.3.4

  were developed and used in the asymmetric addition of α-diazomethylphosphonates to vinylogous imines formed in situ from sulfonylindoles. This methodology tolerates a broad scope of 2-unsubstituted sulfonyl indoles, which have seldom achieved high enantioselectivities in similar asymmetric reactions with other nucleophiles. Chiral 3-sec-alkyl-substituted indoles containing α-diazophosphonate were afforded

  开发了一系列基于 BINAP 的三官能单鏻相转移催化剂，并用于将 α-重氮甲基膦酸酯不对称加成到由磺酰基吲哚原位形成的乙烯基亚胺中。这种方法可以容忍广泛的 2-未取代的磺酰基吲哚，它们在与其他亲核试剂的类似不对称反应中很少实现高对映选择性。以高达 99% 的产率和 95% 的ee提供了含有 α-重氮膦酸盐的手性 3 - sec-烷基取代的吲哚。