Synthesis and Applications of Tricarbonyliron Complexes of Dendralenes |
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| Authors: | Henry Toombs‐Ruane Nik Osinski Dr Thomas Fallon Cindy Wills Dr Anthony C Willis Prof Michael N Paddon‐Row Assoc Prof Michael S Sherburn |
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| Institution: | 1. Research School of Chemistry, Australian National University, Canberra, ACT 0200 (Australia), Fax: (+61)?2‐6125‐8114 http://rsc.anu.edu.au/research/sherburn.php, (synthetic);2. Correspondence author for crystallographic data.;3. School of Chemistry, The University of New South Wales, Sydney, NSW 2052 (Australia), (computational) |
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| Abstract: | 3]Dendralene and 4]dendralene are converted smoothly into tricarbonyliron complexes. The structures of four complexes analyzed by DFT and single‐crystal X‐ray analysis show that, in contrast to free hydrocarbons, complexed dendralenes prefer a roughly in‐plane conformation. The complexes are stable towards Fe(CO)3 group migration up to 150 °C. The synthetic value of Fe(CO)3 complexation in the dendralene series is demonstrated through a variety of selective synthetic manipulations (Diels–Alder reaction, dipolar cycloaddition, Simmons–Smith cyclopropanation, dihydroxylation, olefin cross metathesis) that are not achievable by direct transformation of the free hydrocarbons. Application to the synthesis of a previously unreported, highly reactive linear/cross‐conjugated hydrocarbon is also described. |
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| Keywords: | dendralenes density functional calculations hydrocarbons metathesis synthesis design |
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