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- Title
Stereochemical Behavior of Pairs of P‐stereogenic Phosphanyl Groups at the Dimethylxanthene Backbone.
- Authors
Škoch, Karel; Daniliuc, Constantin G.; Müller, Marcel; Grimme, Stefan; Kehr, Gerald; Erker, Gerhard
- Abstract
The P‐stereogenic bis(phosphanes) 7 and 9, featuring pairs of P(Mes)‐ethynyl or vinyl substituents at the dimethyl xanthene backbone show rather low barriers of stereochemical inversion at phosphorus. π‐Conjugative effects are probably causing these low inversion barriers. Compound 7 reacted with B(C6F5)3 to form the nine‐membered heterocyclic product 10, featuring a [P]−C≡C−B(C6F5)3 substituent. Compound 7 was converted to the bis[P(Mes)vinyl] xanthene derivative 9, which gave the zwitterionic P(H)(Mes)−CH=CH−B(C6F5)3 containing product 16 upon treatment with B(C6F5)3. Thermally induced epimerization barriers at phosphorus of ca. 20 to 27 kcal mol−1 were calculated by DFT for the alkenyl‐ and alkynyl‐P derived systems 6 to 9, 15 and 16 and experimentally determined for the examples 7 and 16.
- Subjects
SPINE; XANTHENE derivatives; EPIMERIZATION; XANTHENE; PHOSPHORUS; PHOSPHINES
- Publication
Chemistry - A European Journal, 2022, Vol 28, Issue 20, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202200248