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Stereoselektive Protonierung von Carbanionen, 2. Diastereoselektive Protonierung von Schöllkopf‐Bislactimether‐Anionen
Author(s) -
Hünig Siegfried,
Klaunzer Norman,
Wenner Hermann
Publication year - 1994
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19941270125
Subject(s) - chemistry , protonation , carbanion , dimer , medicinal chemistry , ether , lewis acids and bases , stereoselectivity , stereochemistry , monomer , solvent , ion , organic chemistry , catalysis , polymer
Stereoselective Protonation of Carbanions, 2 [1] . — Diastereoselective Protonation of Schöllkopf's Bislactim Ether Anions The anions of the bis‐lactim ethers 5–7 serve as models for a systematic investigation of diastereoselective protonation. From 5 Li , 6 Li , and 7 Li in THF at −78°C 30 proton sources (OH, NH, SH, CH) of different acidity and bulkiness produce the following cis / trans ratios: 5 8:92 → 37:63; 6 15:85 → 48:52; 7 25:75 → 59:41 (equilibria ≈ 50:50). Substitution of R 1 = i Pr in 5 by Me (→ 6) decreases the stereoselectivity slightly, but substitution of OMe in 6 by OEt ( 7 ) much stronger (Table 1). Most of the added Lewis acids show week or even leveling effects, whereas with 5 K a dramatic change is observed with cis / trans ‐ 5 = 27:73 → 89:11 (Table 2). By variation of solvent and several additives only minor effects on the cis / trans ratio are observed (Table 3). Backed by 13 CNMR spectra of the ion pairs and literature data protonation of 5 Li ‐ 7 Li is supposed to occur on a dimer, which will mainly react to give trans ‐ 5–7 . The prevailing formation of cis ‐ 5 from 5 K is explained by the reaction of the monomeric ion aggregat.