Formation of Seven-Membered Rings by Ring-Closing Metathesis of Vinyl Bromides

Vachiraporn Ajavakom; Potchanee Pandokrak; Sofia S. Salim; Gamal A. I. Moustafa; Richard K. Bellingham; Joseph T. Hill-Cousins; Anawat Ajavakom; Richard C. D. Brown

doi:10.1055/a-1845-4195

Synlett, Table of Contents

Synlett 2022; 33(14): 1453-1457
DOI: 10.1055/a-1845-4195

cluster

Organic Chemistry in Thailand

Formation of Seven-Membered Rings by Ring-Closing Metathesis of Vinyl Bromides

Vachiraporn Ajavakom∗

^aDepartment of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ramkhamhaeng University, Bangkok 10240, Thailand

,

Potchanee Pandokrak

^aDepartment of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ramkhamhaeng University, Bangkok 10240, Thailand

,

Sofia S. Salim

^bSchool of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, UK

,

Gamal A. I. Moustafa

^bSchool of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, UK

,

Richard K. Bellingham

^cSynthetic Chemistry Department, Chemical Development, GlaxoSmithKline Pharmaceuticals, Old Powder Mills, Tonbridge, Kent, TN11 9AN, UK

,

Joseph T. Hill-Cousins

^bSchool of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, UK

,

Anawat Ajavakom

^dNanotec-CU Center of Excellence on Food and Agriculture, Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand

,

Richard C. D. Brown∗

^bSchool of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, UK

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Abstract

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Abstract

A Grubbs II catalyst mediated ring-closing metathesis (RCM) of monobrominated dienes is reported to proceed in moderate to good yields (40–80%) where the linking chain contains five atoms, leading to carbocyclic and heterocyclic seven-membered bromoolefins. Notably, RCM to form five-, six-, or eight-membered bromoolefins was unsuccessful, with the exception of one example where RCM afforded diethyl 3-bromocyclohex-3-ene-1,1-dicarboxylate. In this case, a bromomethyl-substituted cyclohexene was obtained as a byproduct. The utility of selected bromoolefin RCM products was demonstrated through their participation in Suzuki–Miyaura reactions. Vinylic halide exchange (Br → Cl) was noted as a side reaction under RCM conditions.

Key words

ring-closing metathesis - Grubbs catalyst - vinylic bromides - carbocycles - heterocycles

Full Text

References

References and Notes

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19 2,7-Dibenzyl-4-bromo-2,3,6,7-tetrahydro-1,2,7-thiadiazepine 1,1-Dioxide (2a); Typical Procedure A solution of GII (6.0 mg, 7.0 μmol) in benzene (2 mL) was added to a solution of compound 1a (31.2 mg, 0.07 mmol) in benzene (5 mL), and the mixture was stirred and degassed for 30 s then refluxed for 18 h. A second portion of the GII (3.0 mg, 3.5 μmol) dissolved in benzene (1 mL) was then added and heating was continued for 18 h. The solution was then concentrated under reduced pressure to afford the crude product as a black oil. Purification by column chromatography [silica gel, EtOAc/hexane (2:98)] gave a white solid; yield: 26 mg (90%); mp 106–108 °C. IR (ATR): 3030, 2919, 1507, 1456, 1359 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.40–7.24 (m, 10 H), 6.24 (t, J = 5.7 Hz, 1 H), 4.52 (s, 2 H), 4.45 (s, 2 H), 4.03 (s, 2 H), 3.60 (d, J = 5.7 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 135.6 (C), 135.3 (C), 130.5 (CH), 128.8 (CH), 128.7 (CH), 128.6 (CH), 128.3 (CH), 128.2 (CH), 122.7 (C), 52.4 (CH₂), 52.1 (CH₂), 44.1 (CH₂). LRMS (ES⁺, MeCN): m/z (%): 431 (100) and 429 (100) [M + Na]⁺. HRMS (ES⁺): m/z [M + Na]⁺ calcd for C₁₈H₁₉ ⁷⁹BrN₂NaO₂S: 429.0242; found: 429.0239.

Supplementary Material

Supporting Information