Alkylative Carbocyclization of ω‐Iodoalkynyl Tosylates with Alkynyllithium Compounds Through a Carbenoid‐Chain Process Leading to (1‐Iodoprop‐2‐ynylidene)tetrahydrofurans and ‐cyclopropanes |
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Authors: | Toshiro Harada Prof. Dr. Daisuke Imaoka Chie Kitano Takahiro Kusukawa Prof. Dr. |
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Affiliation: | Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo‐ku, Kyoto 606‐8585 (Japan), Fax: (+81)?75‐724‐7580 |
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Abstract: | Alkylative carbocyclization reactions of ω‐iodoalkynyl tosylates with alkynyllithium compounds to give products with incorporated iodine atoms are described. Slow addition of 2‐(3‐iodoprop‐2‐ynyloxy)ethyl tosylates to 1‐alkynyllithium compounds in tetrahydrofuran at 40 °C followed by additional stirring at this temperature gives (Z)‐3‐(1‐iodoprop‐2‐ynylidene)tetrahydrofurans stereoselectively in good to moderate yields. Under similar conditions at 0 °C, 4‐iodobut‐1‐ynyl tosylates react with 1‐alkynyllithium compounds to give (1‐iodoprop‐2‐ynylidene)cyclopropanes. The carbocyclization reactions are proposed to proceed through a new carbenoid‐chain process involving the exo cyclization of a lithium acetylide intermediate and the vinylic substitution of the resulting TsO,Li‐cycloalkylidenecarbenoids (Ts=tosyl) by 1‐alkynyllithium compounds. |
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Keywords: | alkynes carbenoids cyclization iodine lithium |
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