O. De Lucchi

A general, selective synthesis of ω-hydroxyethenyl ethers

A general selective synthesis of β-, γ- and δ-hydroxyethenyl ethers, a class of compounds containing two mutually reactive functionalities positioned at an interacting distance, is based on the reaction of diols with 1,2-bis-(phenylsulfonyl)ethylene (BPSE) followed by reductive elimination of the resulting β-phenylsulfonyl acetals with sodium amalgam.

Dienophilic and dipolar additions to bicyclo[2.1.0]pent-2-ene

Abstract The dienophiles triazolinedione, singlet oxygen and in part tetracyanoethylene cyclo-add to bicyclo[2.1.0]pent-2-ene (1) across the central σ-bond to give bicyclo[2.2.1]heptene-type adducts, while the dipoles phenyl azide, benzonitrile oxide and diphenyldiazomethane cyclo-add at the π-bond with expected exo stereochemistry.

Crystal structure of 2α-(1,2-dibromoisopropyl)-5a-nitro-5ß-methyl- 1,3-dioxane, C8H13NO4Br2

C8Hi3Br2N04, monoclinic, P12i 1 (No. 4), a = 6.279(2) Ä, b = 9.308(3) Ä, c = 10.219(3) Ä, β = 90.00(5)°, V= 597.2 Ä, Ζ = 2, Rgl(F) = 0.058, wRref(F) = 0.160, T= 293 K. Source of material To a solution of 2-methyl-2-nitro-1,3-propanediol (6.75 g, 50 mmol) in concentrated H2SO4 (8.4 mL, 125 mmol), a solution of HBr (48%, 16.8 mL, 148 mmol) and H2SO4 (98%, 4 mL, 755 mmol) was added dropwise at 273 K. The reaction mixture was heated to 343 Κ and kept at this temperature for 18 h. The colorless solid that separated was filtered, dissolved in ether, washed with 10% NaHCCb, dried over Na2SC>4 and evaporated to afford a solid which was recrystallized from ether (2.5 g, 15% yield). Atom Site X y ζ t/i«, H(1A) 2a 0.0492 0.684 0.2294 0.068 H(IB) la 0.0498 0.6153 0.3697 0.068 H(3) 2a 0.3908 0.9182 0.2707 0.046 H(4A) la 0.4517 1.1710 0.2504 0.050 H(4B) 2a 0.2680 1.2754 0.2931 0.050 H(6A) 2 a 0.1564 1.0196 -0.0177 0.057 H(6B) la 0.3789 1.0065 0.0512 0.057 H(7A) la 0.4516 1.2616 0.0083 0.075 H(7B) la 0.3010 1.3805 0.0652 0.075 H(7C) la 0.2284 1.2891 -0.0557 0.075 H(8A) la 0.3901 0.7888 0.5005 0.075 H(8B) la 0.1673 0.7765 0.5687 0.075 H(8C) la 0.2627 0.9281 0.5366 0.075 Discussion The substituted 1,3-dioxane ring adopts a chair conformation, with puckering parameters [ 1 ] QT = 0.539(8) Ä and Θ2 = 1.5(8)°. In the packing mode of the title compound short C—H—O intermolecular contacts are observed between the 0 3 and 0 4 atoms of the nitro group and the Η atoms linked to the C6, C7 and C8 atoms, with C—O distances in the range 3.263(10) Ä 3.646(12) A and H---0 distances ranging from 2.54 to 2.7 4Ä. * Correspondence author (e-mail: biop02@chor.unip.it)

Crystal structure of (M)-1-{2-hydroxy-3-[(1R,2S,5R)-1-hydroxy-2-isopropyl- 5-methylcyclohexylmethyl]-1-naphthyl}-3-[(1R,2S,5R)-1-hydroxy-2- isopropyl-5-methylcyclohexylmethyl]-2-naphthol, [(C11H7)(C11H18)(OH)2]2

Source o f material: The title compound was prepared by reaction o f (rac)-2,6-di(chIoromethyl)-4,4-dimethyldinaphtho[2,l-d: 1,2-/1[1,3,2]dioxasilepine and ( ) -menthone with samarium diiodide in THF, followed by quenching with aqueous hydrochlorid acid. Rash-chromatography (eluant AcOEt/hexane 1:9). Recrystallization from AcOEt/hexane o f the second eluate gave colorless prisms in 4 5 % yield.

Crystal structure of (2R,3R,5R)-5-(1-iodo-1-methylethyl)-3-(5-(1R,2R,5R)- 5-(1-iodo-1-methylethyl)-2-methyI-3-oxocyclohexyl)-2-furyl)-2-methylcyclohexan- 1-one, C24H34O3I2

H(3) Sb 0.46642 0.43593 0.40906 0.08 H(4) Sb 0.3938(5) 0.3101(5) 0.2831(4) 0.08 H(5A) Sb 0.2356(5) 0.3597(5) 0.2734(4) 0.08 H(5B) ib 0.2548(5) 0.2678(5) 0.2087(4) 0.08 H(6) Zb 0.1616(4) 0.2694(4) 0.3887(5) 0.08 H(7A) 8b 0.1893(5) 0.1007(5) 0.2724(5) 0.08 H(7B) 8i> 0.1452(5) 0.1025(5) 0.3791(5) 0.08 H(9) 8ft 0.3811(6) 0.1410(5) 0.2713(5) 0.08 H(IOA) ib 0.5190(5) 0.1847(6) 0.3570(7) 0.08 H(IOB) Sb 0.4833(5) 0.0812(6) 0.3864(7) 0.08 H(IOC) 8¿. 0.4629(5) 0.1691(6) 0.4563(7) 0.08 H(12A) Sb -0.0702(7) 0.2094(7) 0.2911(7) 0.08 H(12B) Sb -0.0150(7) 0.2149(7) 0.3921(7) 0.08 H(12C) ib 0.0058(7) 0.1299(7) 0.3186(7) 0.08 H(13A) %b -0.0211(6) 0.3747(6) 0.2527(8) 0.08 H(13B) ib 0.0896(6) 0.3973(6) 0.2444(8) 0.08 H(13C) Sb 0.0409(6) 0.3883(6) 0.3486(8) 0.08