ISSN:
1434-1948
Schlagwort(e):
Ansa compounds
;
Cp-derived chelate ligands
;
Neopentane chemistry
;
Spiro compounds
;
Tripodal ligands
;
Cyclopentadienyl compounds
;
Chemistry
;
General Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
The neopentane-derived functionalized oxetane O(CH2)2C(CH3)(CH2OMs), 1, reacts with indenyllithium (LiInd) or fluorenyllithium (LiFlu) to produce the derivatives O(CH2)2C(CH3)(CH2R) (R = indenyl, fluorenyl), 2. The oxetane ring of 2 undergoes nucleophilic ring-opening by reaction with LiPR′2 to give the chiral chelate ligands (HOCH2)(CH3)C(CH2R)(CH2PR′2) (R = indenyl, fluorenyl), 5. Nucleophilic ring-opening by LiInd or LiFlu is possible too, resulting in the functionalized ansa-Cp ligands (HOCH2)(CH3)C(CH2R)(CH2R′) (R, R′ = indenyl, fluorenyl), 12. Electrophilic ring-opening of 2 with HBr to give (HOCH2)(CH3)C(CH2R)(CH2Br) (R = indenyl, fluorenyl), 3, is also possible. The alcohol function of 3 may be activated directly, whereas activation of this group in 5 is only possible after BH3 protection of the phosphane function. The mesylates (MsOCH2)(CH3)C(CH2R)(CH2Br) (R = indenyl, fluorenyl), 4, undergo, under basic conditions, spiro cyclization to produce spirocyclobutane derivatives 9 with the α-carbons of the five-membered cycles acting as the spiro centres. Substitution of the mesylate group of 4 by PR2 nucleophiles is therefore not possible. Ansa-Cp derivative (MsOCH2)(CH3)C(CH2Ind)(CH2Flu), 12c also reacts with LiPPh2 with spiro cyclization to produce 9d, instead of giving the substitution product. Tripodal ligands (CH3)C(CH2R)(CHPPh2)2 (R = indenyl, fluorenyl), 11, are accessible by the reaction of (MsOCH2)(CH3)C(CH2PPh2)2 with LiInd or LiFlu. All compounds are fully characterized by the usual spectroscopic and analytical techniques including single-crystal X-ray analyses in several cases.
Zusätzliches Material:
6 Ill.
Materialart:
Digitale Medien
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