| Autor: |
Begum S; Department of Organic Chemistry, Indian Institute of Science, Bengaluru 560012, India., Bhattacharya R; Department of Organic Chemistry, Indian Institute of Science, Bengaluru 560012, India., Paul S; Department of Organic Chemistry, Indian Institute of Science, Bengaluru 560012, India., Chakraborty TK; Department of Organic Chemistry, Indian Institute of Science, Bengaluru 560012, India. |
| Jazyk: |
angličtina |
| Zdroj: |
The Journal of organic chemistry [J Org Chem] 2023 Sep 01; Vol. 88 (17), pp. 12677-12697. Date of Electronic Publication: 2023 Aug 22. |
| DOI: |
10.1021/acs.joc.3c01356 |
| Abstrakt: |
A systematic study is undertaken to investigate the less explored endo-trig radical cyclization in activated olefin-appended epoxides using Cp 2 TiCl. The radical generated by the Ti(III)-promoted reductive opening of the epoxy ring promptly underwent endo-trig cyclization, giving access to differently 1,3-disubstituted six- and seven-membered carbocycles in good yields and diastereoselectivity. This protocol was successfully employed in the construction of 5,7- and 6,7-fused bicyclic frameworks entailing a de novo synthesis of (±)-isoclavukerin A belonging to tri- nor -guaiane class of sesquiterpene natural products in eight simple steps from commercially available starting materials. Besides the Ti(III)-mediated reaction serving as a key step in the synthesis, a sequential [2,3]-sigmatropic rearrangement/syn-elimination of an allyl sulfenate intermediate successfully rendered the highly constrained diene moiety in the hydroazulene core of the target molecule. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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