ChemInform Abstract: Synthesis and Properties of 1,3‐Dithiole(3)‐ and (4)dendralenes, Acyclic Systems of the Corresponding (3)‐ and (4)Radialenes.

Misaki, Yohji; Matsumura, Yoshihiro; Sugimoto, Toyonari; Yoshida, Zen‐ichi

doi:10.1002/chin.199019180

Cited by 1 publication

(4 citation statements)

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“…Overall, the product distribution obtained from reaction of 1E-methyl [4]dendralene (10) with NMM correlates closely with that of the parent [4]dendralene (1). Similar yields of analogous products are obtained, in spite of the additional complexity brought to bear on the system by the methyl substituent.…”

Section: ■ Introductionmentioning

confidence: 60%

“…1E-Methyl [4]dendralene (10). A freshly prepared solution of (3methylenepenta-1,4-dien-2-yl)magnesium chloride (63) (25 mL, 0.16 M solution in THF, 4.0 mmol, 1.6 mol equiv) was added slowly into a stirred solution of ZnBr 2 (0.92 g, 4.1 mmol, 1.6 mol equiv) and THF (5.0 mL) at 0 °C.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Purification by flash column chromatography (SiO 2 , EtOAc:hexane (70:30)) gave the title compound 26 (2.5 g, 16 mmol, 91% yield) as a yellow oil. R f 0.26 (EtOAc:hexane (70:30)); 1 H NMR (300 MHz, CDCl 3 ) δ 5.43 (q, J = 6.9 Hz, 1H), 5.11 (d,J = 1.3 Hz,1H),4.81 (d,J = 2.3 Hz,1H),3.62 (dt,J = 13.2,6.3 Hz,4H), 2.42 (br s, 2H), 2.38 (t, J = 6.5 Hz, 2H), 2.32 (t, J = 6.3 Hz, 2H), 1.63 (d, J = 6.7 Hz, 3H) ppm; 13 C NMR (75 MHz, CDCl 3 ) δ 144.1 (C), 138.5 (C), 124.1 (CH), 115.9 (CH 2 ), 60.9 (CH 2 ), 60.8 (CH 2 ), 39.6 (CH 2 ), 38.6 (CH 2 ), 14.7 (CH 3 ) ppm; IR (thin film) ν max = 3339, 2936, 2882, 1441, 1045 cm −1 ; LRMS (70 eV, EI) m/z (%) 156 ([M] +• , 4%), 138 (10), 126 (36), 111 (71), 97 (100); HRMS calc for C 9 H 16 O 2 [M] +• 156.1150, found 156.1150.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…When 1E-methyl [4]dendralene (10) was treated with an excess 30 (3 mol equiv) of NMM at room temperature, five different products were formed (Scheme 4): a single internal monoadduct 29 in 14% yield, two bis-adducts 32 and 33 in 7% and 48% yields, both as single diastereomers, and two diastereomeric tris-adducts 36 and 37 in a 1:1 ratio (20% yield). 31 Upon the basis of this product distribution we can determine that the first cycloaddition reaction proceeds with ca.…”

Section: ■ Introductionmentioning

confidence: 99%

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Synthesis and Diels–Alder Reactivity of Substituted [4]Dendralenes

et al. 2016

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The first synthesis of all five possible monomethylated [4]dendralenes has been achieved via two distinct synthetic strategies. The Diels-Alder chemistry of these new dendralenes (as multidienes) with an electron poor dienophile, N-methylmaleimide (NMM), has been studied. Thus, simply upon mixing the dendralene and an excess of dienophile at ambient temperature in a common solvent, sequences of cycloadditions result in the rapid generation of complex multicyclic products. Distinct product distributions are obtained with differently substituted dendralenes, demonstrating that dendralene substitution influences the pathway followed, when a matrix of mechanistic possibilities exists. Dendralene site selectivities are traced to electronic, steric and conformational effects, thereby allowing predictive tools for applications of substituted dendralenes in future synthetic endeavors.

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Section: ■ Introductionmentioning

confidence: 60%

Section: ■ Experimental Sectionmentioning

confidence: 99%