Gock Michael, Lutter Michael, Pintus Anna, Schollmeier Dieter, Arca Massimiliano, Lippolis Vito, Jurkschat Klaus
Technische Universität Dortmund, Fakultät für Chemie und Chemische Biologie, 44221, Dortmund, Germany.
Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554, Bivio per Sestu, 09042, Monserrato (CA), Italy.
Chemistry. 2022 Oct 18;28(58):e202201447. doi: 10.1002/chem.202201447. Epub 2022 Aug 26.
The sequence of reactions of the phosphorus-containing aryllithium compound 5-t-Bu-1,3-[(P(O)(O-i-Pr) ] C H Li (ArLi) with Ph PCl, KMnO , elemental sulfur and elemental selenium, respectively, gave the aryldiphenylphosphane chalcogenides 5-t-Bu-1,3-[(P(O)(O-i-Pr) ] C H P(E)Ph (1, E=O; 2, E=S; 3, E=Se). Compound 1 partially hydrolysed giving [5-t-Bu-1-{(P(O)(O-i-Pr) }-3-{(P(O)(OH) }C H ]P(O)Ph (4). The reaction of ArLi with PhPCl provided the benzoxaphosphaphosphole [1(P), 3(P)-P(O)(O-i-Pr)OPPh-6-t-Bu-4-P(O)(O-i-Pr) ]C H P (5i) as a mixture of the two diastereomers. The oxidation of 5i with elemental sulfur gave the benzoxaphosphaphosphole sulfide [1(P), 3(P)-P(O)(O-i-Pr)OP(S)Ph-6-t-Bu-4-P(O)(O-i-Pr) ]C H (5) as pair of enantiomers P1(R), P3(S)/P1(S), P3(R) of the diastereomer (RS/SR)-5 (5b). The aryldiphenylphosphane 5-t-Bu-1,3-[(P(O)(O-i-Pr) ] C H PPh (6) was obtained from the reaction of the corresponding aryldiphenylphosphane sulfide 2 with either sodium hydride, NaH, or disodium iron tetracarbonyl, Na Fe(CO) . The oxidation of the aryldiphenylphosphane 6 with elemental iodine and subsequent hydrolysis yielded the aryldiphenyldioxaphosphorane 9-t-Bu-2,6-(OH)-4,4-Ph -3,5-O -2,6-P -4λ -P-[5.3.1.0]-undeca-1(10),7(11),8-triene (7). Both of its diastereomers, (RR/SS)-7 (7a) and (RS/SR)-7 (7b), were separated as their chloroform and i-propanol solvates, 7a⋅2CHCl and 7b⋅i-PrOH, respectively. DFT calculations accompanied the experimental work.
含磷芳基锂化合物5-叔丁基-1,3-[(P(O)(O-i-Pr))]C₆H₃Li（ArLi）分别与Ph₂PCl、KMnO₄、元素硫和元素硒发生反应，得到芳基二苯基膦硫属化物5-叔丁基-1,3-[(P(O)(O-i-Pr))]C₆H₃P(E)Ph（1，E = O；2，E = S；3，E = Se）。化合物1部分水解生成[5-叔丁基-1-{(P(O)(O-i-Pr))}-3-{(P(O)(OH))}C₆H₂]P(O)Ph（4）。ArLi与PhPCl反应得到苯并氧磷磷杂环戊二烯[1(P), 3(P)-P(O)(O-i-Pr)OPPh-6-叔丁基-4-P(O)(O-i-Pr)]C₆H₂P（5i），为两种非对映异构体的混合物。5i与元素硫氧化反应得到苯并氧磷磷杂环戊二烯硫化物[1(P), 3(P)-P(O)(O-i-Pr)OP(S)Ph-6-叔丁基-4-P(O)(O-i-Pr)]C₆H₂（5），为非对映异构体（RS/SR）-5（5b）的对映体P1(R), P3(S)/P1(S), P3(R)。芳基二苯基膦5-叔丁基-1,3-[(P(O)(O-i-Pr))]C₆H₃PPh（6）由相应的芳基二苯基膦硫化物2与氢化钠（NaH）或四羰基二钠铁（Na₂Fe(CO)₄）反应制得。芳基二苯基膦6与元素碘氧化反应并随后水解得到芳基二苯基二氧磷杂环戊烷9-叔丁基-2,6-(OH)-4,4-Ph₂-3,5-O₂-2,6-P-4λ⁵-P-[5.3.1.0]-十一碳-1(10),7(11),8-三烯（7）。其两种非对映异构体，（RR/SS）-7（7a）和（RS/SR）-7（7b），分别以它们的氯仿和异丙醇溶剂化物7a⋅2CHCl和7b⋅i-PrOH形式分离出来。密度泛函理论计算辅助了实验工作。
