Tert-butyl-[(1,3-dimethyl-1,3,2-diazaphospholidin-2-yl)oxy]-dimethylsilane | 160622-55-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Tert-butyl-[(1,3-dimethyl-1,3,2-diazaphospholidin-2-yl)oxy]-dimethylsilane
• CAS: 160622-55-9
• 化学式: C₁₀H₂₅N₂OPSi
• 分子量: 248.381
• InChiKey: OJGIELCAODQVCY-UHFFFAOYSA-N

物化性质

• 沸点：
  252.348±23.00 °C(Press: 760.00 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.11
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 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 、 Tert-butyl-[(1,3-dimethyl-1,3,2-diazaphospholidin-2-yl)oxy]-dimethylsilane 以 二氯甲烷 为溶剂， 反应 4.0h， 以80%的产率得到2-[(S)-(tert-Butyl-dimethyl-silanyloxy)-phenyl-methyl]-1,3-dimethyl-[1,3,2]diazaphospholidine 2-oxide
  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：

  叔丁基二甲基硅烷醇 、 2-chloro-1,3-dimethyl-1,3,2-diazaphospholidine 在 三乙胺 作用下， 以 甲苯 为溶剂， 反应 3.5h， 以76%的产率得到Tert-butyl-[(1,3-dimethyl-1,3,2-diazaphospholidin-2-yl)oxy]-dimethylsilane
  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.