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Novel Nine‐Membered Titanaheterocycles – Structure, ab initio Calculations, and Preparative Use towards the Selective Synthesis of Substituted Cyclopentanols
Author(s) -
Hampel Frank,
van Eikema Hommes Nico,
Hoops Sven,
Maaref Faramarz,
Schobert Rainer
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199809)1998:9<1253::aid-ejic1253>3.0.co;2-h
Subject(s) - chemistry , cyclopentadienyl complex , ab initio , yield (engineering) , ab initio quantum chemistry methods , computational chemistry , crystal structure , hydrolysis , coupling reaction , medicinal chemistry , organic chemistry , catalysis , molecule , materials science , metallurgy
Reactions of Cp 2 Ti(CO) 2 ( 3 ) with two equivalents of α,β‐unsaturated ketones 4 yield the novel titana‐2,9‐dioxacyclonona‐3,7‐dienes 5 . Cross‐coupling of 3 with two different ketones 4 and 6 to give 7 can be achieved under certain reaction conditions. Hydrolysis of 5 or 7 may generate diketones 9 , cyclopentanols 10 / 11 , or cyclopentenes 12 / 13 , depending on substituents and conditions. The X‐ray crystal structure of 5a , the first nine‐membered bis(η 5 ‐cyclopentadienyl)‐substituted titanaheterocycle containing carbon, is presented. Ab initio calculations were performed for 5a and for titana‐2‐oxacyclopentene 1 , a conceivable intermediate in the coupling reaction.