Hydrodeoxygenative Cyclotetramerization of Carbon Monoxide by a Trinuclear Titanium Polyhydride Complex.
J Am Chem Soc
; 142(47): 19889-19894, 2020 Nov 25.
Article
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| ID: mdl-33170679
ABSTRACT
The reductive coupling of carbon monoxide (CO) by metal hydrides is of fundamental interest and practical importance. Herein we report an unprecedented hydrodeoxygenative cyclotetramerization of CO by a trinuclear titanium polyhydride complex [(C5Me4SiMe3)Ti]3(µ3-H)(µ2-H)6 (1). The reaction of CO with 1 at -78 °C gave an ethen-1,2-diyl species [CHâCH]2- through the hydrodeoxygenative dimerization of two molecules of CO, which upon cycloaddition to another two molecules of CO afforded a cyclobuten-3,4-diyl-1,2-diolate unit [C4H2O2]4-. The hydrogenolysis of the [C4H2O2]4- species with H2 yielded a tetrahydrocyclobuten-1,2-diolate species [C4H4O2]2-, which on heating at 100 °C gave a cyclobuten-2-yl-1-olate product [C4H4O]2-. The acidolysis of the [C4H2O2]4- and [C4H4O]2- species with HCl afforded γ-butyrolactone and cyclobutanone, respectively.
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Bases de datos:
MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
Año:
2020
Tipo del documento:
Article
País de afiliación:
Japón