(1,3-Dimethyl-1,3,2-diazaphosphinan-2-yl)oxy-triphenylsilane | 160622-68-4

• 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: (1,3-Dimethyl-1,3,2-diazaphosphinan-2-yl)oxy-triphenylsilane
• CAS: 160622-68-4
• 化学式: C₂₃H₂₇N₂OPSi
• 分子量: 406.539
• InChiKey: WFHUJAXMFSMIEW-UHFFFAOYSA-N

物化性质

• 沸点：
  476.235±28.00 °C(Press: 760.00 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.16
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  15.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  苯甲醛 、 (1,3-Dimethyl-1,3,2-diazaphosphinan-2-yl)oxy-triphenylsilane 以 二氯甲烷 为溶剂， 反应 2.5h， 以52%的产率得到[(1,3-Dimethyl-2-oxo-1,3,2lambda5-diazaphosphinan-2-yl)-phenylmethoxy]-triphenylsilane
  参考文献：
  名称：

  Carbonyl phosphonylation via[1 N ,3 E ]-bifunctional reagents. Probing mechanistic and reactivity features through chemical and isotopic labelling

  摘要：

  A range of organophosphorus(III) esters of the general form {DIAM}PX(SiR(3))(n){X = 0, n = 1; X = N, n = 2; R(3) = Me(3), Ph(3), (t)BuMe(2), Et(3); DIAM = N,N'-(CH(2)NMe)(2) and N,N'-CH2(CH(2)NMe)(2)} has been prepared via reaction of {DIAM}PCl with R(3)SiOH or LiN(SiMe(3))(2) respectively. These esters will phosphonylate aldehydes via the Abramov reaction to afford alpha-siloxyphosphonate esters cleanly and in high yields. The mechanism of the Abramov reaction using {DIAM}POSiR(3) reagents has been investigated by (i) O-18 isotopic labelling experiments which reveal that reaction proceeds with exclusive [O-Si] rather than [P-O] bond cleavage which, in turn, supports a mechanism with overall retention of configuration at phosphorus, (ii) double crossover experiments which support intramolecular silyl-group transfer and (iii) manipulations of the electron-donating properties of the carbonyl substrate which suggest that [P-C] bond formation is rate determining. Further tuning of the phosphonylation reaction is possible by manipulating (a) the nature of the phosphorus-coordinated donor atoms in the chelate ring. (b) the size and rigidity of the chelate ring. (c) the ester residue donor atom X and (d) the silicon substituents R.

  DOI：

  10.1039/p19940003169
• 作为产物：
  描述：

  N,N'-二甲基-1,3-丙二胺 在 三乙胺 、 三氯化磷 作用下， 以 甲苯 为溶剂， 反应 6.5h， 生成 (1,3-Dimethyl-1,3,2-diazaphosphinan-2-yl)oxy-triphenylsilane
  参考文献：
  名称：

  Carbonyl phosphonylation via[1 N ,3 E ]-bifunctional reagents. Probing mechanistic and reactivity features through chemical and isotopic labelling

  摘要：

  A range of organophosphorus(III) esters of the general form {DIAM}PX(SiR(3))(n){X = 0, n = 1; X = N, n = 2; R(3) = Me(3), Ph(3), (t)BuMe(2), Et(3); DIAM = N,N'-(CH(2)NMe)(2) and N,N'-CH2(CH(2)NMe)(2)} has been prepared via reaction of {DIAM}PCl with R(3)SiOH or LiN(SiMe(3))(2) respectively. These esters will phosphonylate aldehydes via the Abramov reaction to afford alpha-siloxyphosphonate esters cleanly and in high yields. The mechanism of the Abramov reaction using {DIAM}POSiR(3) reagents has been investigated by (i) O-18 isotopic labelling experiments which reveal that reaction proceeds with exclusive [O-Si] rather than [P-O] bond cleavage which, in turn, supports a mechanism with overall retention of configuration at phosphorus, (ii) double crossover experiments which support intramolecular silyl-group transfer and (iii) manipulations of the electron-donating properties of the carbonyl substrate which suggest that [P-C] bond formation is rate determining. Further tuning of the phosphonylation reaction is possible by manipulating (a) the nature of the phosphorus-coordinated donor atoms in the chelate ring. (b) the size and rigidity of the chelate ring. (c) the ester residue donor atom X and (d) the silicon substituents R.

  DOI：

  10.1039/p19940003169

文献信息

• Carbonyl phosphonylation via[1 N ,3 E ]-bifunctional reagents. Probing mechanistic and reactivity features through chemical and isotopic labelling
  作者：Paul G. Devitt、Terence P. Kee

  DOI：10.1039/p19940003169

  日期：——

  A range of organophosphorus(III) esters of the general form DIAM}PX(SiR(3))(n)X = 0, n = 1; X = N, n = 2; R(3) = Me(3), Ph(3), (t)BuMe(2), Et(3); DIAM = N,N'-(CH(2)NMe)(2) and N,N'-CH2(CH(2)NMe)(2)} has been prepared via reaction of DIAM}PCl with R(3)SiOH or LiN(SiMe(3))(2) respectively. These esters will phosphonylate aldehydes via the Abramov reaction to afford alpha-siloxyphosphonate esters cleanly and in high yields. The mechanism of the Abramov reaction using DIAM}POSiR(3) reagents has been investigated by (i) O-18 isotopic labelling experiments which reveal that reaction proceeds with exclusive [O-Si] rather than [P-O] bond cleavage which, in turn, supports a mechanism with overall retention of configuration at phosphorus, (ii) double crossover experiments which support intramolecular silyl-group transfer and (iii) manipulations of the electron-donating properties of the carbonyl substrate which suggest that [P-C] bond formation is rate determining. Further tuning of the phosphonylation reaction is possible by manipulating (a) the nature of the phosphorus-coordinated donor atoms in the chelate ring. (b) the size and rigidity of the chelate ring. (c) the ester residue donor atom X and (d) the silicon substituents R.