ChemInform Abstract: PHOSPHORYLATED ADAMANTANES. I. PHOSPHORYLATION OF 1‐ AND 2‐HYDROXYADAMANTANE BY PHOSPHORUS(III) ACID CHLORIDES

Abstract

1‐Hydroxyadamantan (Ia) bzw. Z‐Hydroxy‐adamantan (Ib) reagieren mit Phosphortrichlorid in Gegenwart von Triethylamin zu den Adamantyl‐dichlorphosphiten (IIa) und (IIb).

Titanium complexes based on chiral enantiopure dialkanolamines: synthesis, structures and catalytic activity

“…The complexes 20,22,23,25,26,28,30 are investigated as catalysts in phospho-aldol addition reaction using diethyl phosphite (Scheme 9, Table 3). The Abramov reaction was carried out in the presence of an amount of catalyst equal to 10 mol%.…”

“…All manipulations with titanium compounds were carried out under an argon atmosphere using standard Schlenk techniques. 23 dimethyl-, diethyl-and di(isopropyl)phosphite, 24 (1-adamanthyl)phosphite, 25 di-(1R,2S,5R)-menthyl chlorophosphite 26 were synthesized according to the literature procedure. C 6 D 5 CD 3 , CDCl 3 were obtained from Deutero GmbH.…”

“…The solvent was evaporated under reduced pressure and the product 24 was isolated after recrystallization at À20 1C from dichloromethane-heptane mixture as a yellow solid (1.10 g, 82%); C 18 H 32 Cl 2 N 2 O 2 Ti requires C, 50.6; H, 7.55; N, 6.6%; found C, 48.8; H, 7.9; N, 6.60%; d H (400.1 MHz, CDCl 3 , ppm) 7.33-7.21 (5H, m, CH arom ), 5.16 (1H, br s, HNMe 2 ), 4.07 (1H, q, J 6.8, NCH), 3.00, 2.93 (each 2H, each d, J 14.9, 2NCH 2 ), 2.64 (6H, s, HN(CH 3 ) 2 ), 1.56 (3H, d, J 6.8, CHCH 3 ), 1.30, 1.15 (each 6H, each s, C(CH 3 ) 2 ); d C (100.61 MHz, CDCl 3 , ppm) 142. 71, 128.40, 128.21, 127.19 (C arom and CH arom ), 95.49 (OCMe 2 ), 67.58, 65.08 (NCH 2 , NCH), 40.03 (HN(CH 3 ) 2 ), 27.42,27.33 (C(CH 3 ) 2 ), 16.36 (CHCH 3 ); m/z (EI) 352 ([M À HNMe 2 À 2CH 3 ] + , 2%), 295 (1), 206 (18), 105 (100), 83 (25); m/z (ESI + ) 383.2 ([M À HNMe 2 ] + ).…”

“…[(R)-PhCH(Me)N(CH 2 C(Me) 2 O) 2 ] 2 Ti (25). Ti(O-i-Pr) 4 (0.54 mL, 1.8 mmol) was added dropwise to a stirred solution of dialkanolamine 10 (0.95 g, 3.6 mmol) in toluene (20 mL).…”

“…Experimental data were collected at 120 K on Bruker SMART 1K diffractometer (for 23,25,28,31) and on Bruker SMART APEX diffractometer (for 26, 27, 30) using Mo-Ka radiation (l = 0.71073 A ˚). Absorption corrections based on measurements of equivalent reflections were applied.…”