Thieme chemistry journal awardees - Where are they now? Diastereoselective tandem iodocarbonate cyclization of 1,5-enynes

Synlett

Volumn , Issue 3, 2010, Pages 368-373

  Lim, Choongmin ^a   Rao, M Shesha ^a   Shin, Seunghoon ^a  

^a Hanyang University   (South Korea)

Author keywords

Diastereoselectivity; Enynes; IBr; Iodocyclization; Tandem reactions

Indexed keywords

ALKENE; ALKYNE; GOLD; IODINE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL ANALYSIS; CHEMICAL REACTION; CYCLIZATION; DIASTEREOISOMER; SYNTHESIS;

EID: 76349111564     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-0029-1219183     Document Type: Article

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43. The structural and stereochemical identity of the iodocarbonate products 4 were confirmed by the conversion of 4f/4g into 7f/7g (Scheme 2), respectively, by the radical deiodination as below. Spectra of 7f/7g matched those of the respective products obtained in Au(I) catalysis.6c For 4o and 4q, relative stereochemistry was based on 1D-NOE spectra
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51. However, in the formation of 4h, 4k, and 4n/5n, diastereomeric products having trans-1,2-vicinal relationship between the two methyl bearing centers were not observed. This observation indicates some degree of concertedness of CC and CO bond formations (or less likely, stereoelectronically driven nucleophilic trapping of the cationic center).
52. Typical Procedure for the IBr-Promoted Tandem Cyclization To a solution of 2f (57.3 mg, 0.200 mmol) in CH2Cl2 (1 mL) at 78 C was added dropwise a solution of IBr (82.7 mg, 0.400 mmol) in CH2Cl2 (1 mL). The mixture was kept stirred at 78 C for 20 min, then aq sat. Na2S2O3 (4 mL) was added at once. The mixture was allowed to warm to r.t. with stirring. Layers were separated, and the aqueous layer was extracted with CH2Cl2 (3 4 mL). The combined organic layers were dried (MgSO4), evaporated, and the residue was purified by silica gel chromatography (EtOAc hexane = 1:6) to yield 57.5 mg (81%) of 4f as a white solid (mp 154156 C). Compound 4f: IR (neat): 2916, 1800, 1436, 1350, 1185, 1057 cm1. 1H NMR (400 MHz, CDCl3): d = 7.457.28 (m, 3 H), 7.287.15 (m, 2 H), 4.60 (t, J = 3.0 Hz, 1 H), 3.32 (dd, J = 2.2, 16.9 Hz, 1 H), 2.97 (dd, J = 2.6, 17.0 Hz, 1 H), 2.93 (d, J = 15.8 Hz, 1 H), 2.52 (d, J = 15.8 Hz, 1 H), 1.60 (s, 3 H). 13C NMR (100 MHz, CDCl3): d = 154.5, 144.5, 144.0, 129.1, 128.6, 128.2, 88.7, 83.6, 82.0, 44.7, 42.7, 26.7. HRMS: m/z calcd for C14H13INaO3 [M + Na]+: 378.9807; found: 378.9809. ompound 4g: white solid; mp 114115 C. IR (neat): 2921, 1790, 1506, 1246, 1052 cm1. 1H NMR (400 MHz, CDCl3): d = 7.18 (d, J = 8.8 Hz, 2 H), 6.89 (d, J = 8.5 Hz, 2 H), 4.58 (t, J = 2.9 Hz, 1 H), 3.82 (s, 3 H), 3.31 (dd, J = 2.2, 16.9 Hz, 1 H), 2.96 (dd, J = 2.5, 16.9 Hz, 1 H), 2.92 (d, J = 15.8 Hz, 1 H), 2.51 (d, J = 15.8 Hz, 1 H), 1.60 (s, 3 H). 13C NMR (100 MHz, CDCl3): d = 159.8, 154.5, 144.0, 136.3, 129.6, 114.3, 88.1, 83.7, 82.0, 55.9, 44.8, 42.9, 26.7. Anal Calcd for C15H15IO4: C, 46.65; H, 3.92. Found: C, 45.60; H, 4.10. LRMS (CI+): m/z calcd for C15H16IO4 [M+ + H]: 387; found: 387 (100) [M+ + H], 343 (6) [M+ + H CO2], 325 (67) [M+ + H CO2 H2O]. Compound 5g: colorless liquid. IR (neat): 2968, 2926, 1738, 1506, 1279, 1246, 1156, 1085 cm1. 1H NMR (400 MHz, CDCl3): d = 7.10 (d, J = 8.4 Hz, 2 H), 6.89 (d, J = 8.8 Hz, 2 H), 5.00 (t, J = 4.7 Hz, 1 H), 3.82 (s, 3 H), 3.44 (d br, J = 18.7 Hz, 1 H), 3.07 (d of ABq, J = 7.9 Hz, 1 H), 3.00 (d of ABq, J = 7.9 Hz, 1 H), 2.94 (d br, J = 18.7 Hz, 1 H), 1.81 (s, 3 H), 1.52 (s, 9 H). 13C NMR (100 MHz, CDCl3): d = 159.6, 153.3, 141.2, 137.9, 129.7, 114.3, 93.1, 83.6, 61.4, 55.9, 47.7, 45.7, 28.8, 28.4. LRMS (CI+): m/z calcd for C19H25 79BrIO4 [M+ + H]: 523; found: 523 (24) [M+ + H, 79Br], 525 (24) [M+ + H, 81Br], 467 (10) [M+ + H C4H8, 79Br], 469 (8) [M+ + H C4H8, 81Br], 443 (6) [M+ 79Br], 405 (37) [M+ + H C4H8 CO2 H2O, 79Br], 407 (36) [M+ + H C4H8 CO2 H2O, 81Br]. Compound 4n: white solid; mp 105107 C. IR (NaCl): 2916, 2850, 1790, 1601, 1511, 1350, 1246, 1057 cm1. 1H NMR (400 MHz, CDCl3): d = 7.12 (d, J = 8.8 Hz, 2 H), 6.90 (d, J = 8.4 Hz, 2 H), 4.55 (t, J = 3.7 Hz, 1 H), 3.82 (s, 3 H), 3.243.16 (m, 2 H), 2.95 (q, J = 7.3 Hz, 1 H), 1.58 (s, 3 H), 1.07 (d, J = 7.3 Hz, 3 H). 13C NMR (100 MHz, CDCl3): d = 159.8, 154.6, 149.6, 136.7, 130.0, 129.8, 114.4, 89.0, 86.0, 81.9, 55.9, 46.3, 43.8, 25.0, 13.4. ES-HRMS: m/z calcd for C16H17IO4Na [M + Na]+: 423.0069; found: 423.0068. Compound 5n: pale yellow liquid. IR (NaCl): 2916, 2930, 1743, 1601, 1506, 1365, 1279, 1242, 1156 cm1. 1H NMR (400 MHz, CDCl3): d = 7.16 (d, J = 8.4 Hz, 2 H), 6.91 (d, J = 8.8 Hz, 2 H), 5.49 (dd, J = 3.3, 7.7 Hz, 1 H), 4.03 (q, J = 6.9 Hz, 1 H), 3.82 (s, 3 H), 3.37 (dd, J = 7.7, 17.3 Hz, 1 H), 2.77 (dd, J = 3.3, 17.2 Hz, 1 H), 1.70 (d, J = 7.0 Hz, 3 H), 1.51 (s, 9 H), 1.14 (s, 3 H). 13C NMR (100 MHz, CDCl3): d = 159.9, 153.6, 152.8, 131.2, 129.5, 114.3, 95.2, 83.1, 78.3, 60.4, 57.4, 55.8, 50.7, 28.4, 21.8, 18.7. LRMS (CI+): m/z calcd for C20H26 79BrIO4 [M+ + H]: 537; found: 537 (22) [M+ + H, 79Br], 539 (22) [M+ + H, 81Br], 481 (26) [M+ + H C4H8, 79Br], 483 (24) [M+ + H C4H8, 81Br], 419 (52) [M+ BocO, 79Br], 421 (51) [M+ BocO, 81Br], 401 (100) [M+ Br C4H8, 79Br].