Reactions of n-sulfinyl-p-toluenesulfonamide with alcohols

N-Sulfinyl p-toluenesulfonamide (1) reacted with triaryl- and diarylmethanols to give predominantly N- substiuted sulfonamides and SO₂ presumably via carbonium ion intermediates. When carbonium ion forming alchols, such as t-BuOH and Ph₂C(Me)OH, were used the predominant products were alkenes and p- toluenesulfonamide. Allytic alcohols afforded N- substiuted sulfonamides along with dienes andp-toluenesulfonamide. Alcohols which could not predictably give relatively stable intermediate carbonium ions, gave either dialkyl sulfites or dialkyl eithers, along with p-toluenesulfonamide. In one case, namely with 9-phenylfluorenol the 1:1 adduct with 1 (an amidosulfite) was isolated. A mechanism for the reactions is proposed.     

Synthesis of a tetracyclodecenone with two orthogonal π-electron systems via a 1,3-through cage elimination in a bridgehead substituted 1,3-bishomocubyl acetate

Stereoselective reduction of 1,3-bishomocubanone acetate $\text{1}$ followed by mesylation leads to an epimeric mixture of mesylates $\text{3}$. Base induced homoketonization of the anti-epimer $\text{3b}$ affords tetracyclo[5.3.0.0^2,5 O^4,8]decenone $\text{4}$.     

Synthesis and Isolation of α-Oxo Sulfines

The synthesis of several α-oxo sulfines is discribed. Various α-oxo sulfines can be isolated as such. The Diels-Alder reaction of these sulfines with 1,3-dienes can be catalyzed by Lewis acids.     

Crystal and molecular structure of rac (1R,5R,6S,7R)-1-oxy-7-benzoyl-5-methyl-8-azabicyclo-[4.3.0]-nonane-4,9-dione, C16H17NO4 (perhydroisoindole)

The structure of the title compound (perhydroisoindole) was determined by X-rays, using CuK radiation (graphite-crystal monochromator, =1.54184 Å):T=290 K, C₁₆H₁₇NO₄,M _r =287.31, orthorhombic, space groupPbcn,a=18.732(1),b=10.663(1),c=14.074(1) 0A,V _c =2811.2 ų,Z=8,D _x =1.361 Mg m^–3 and (CuK)=8.19 cm^–1. The final conventionalR-factor=0.036, (R _w =0.046) for 1951 unique reflections and 241 variables. The structure was solved usingMultan. The six-membered ring of the molecule is in the chair configuration. The molecules are connected by hydrogen bonds.     

Regio- and stereospecific ring-opening reactions of 4-substituted basketanes and seco-basketanes

Homoketonization of basketane acetates6 and 10 on brief treatment with NaOMe in MeOH afforded the seco-basketanones7 and11, respectively, in a stereo-and regiospecific cage opening reaction. As shown by deuterium labeling experiments, both for 6 and 10, this homoketonization proceeds with retention of configuration. Prolonged basic treatment of10 led to the exclusive formation of bicyclo[2.2.2]octenyl-acetates12. Under identical conditions6 produced a complex mixture of products. Upon treatment of seco-basketanones7 and 11 with aq HC1 in MeOH, a rapid regiospecific cationic rearrangement to homobrendanone 14 was observed. This structure was established by X-ray analysis. The effect of a one carbon cage expansion on the base induced cage opening process by extension of the methylene bridge in the homocubane system into an ethylene bridge in the basketane system, is discussed.     

Oxygen transfer during the copper induced reaction of α,β-epoxy diazomethyl ketones

Reactions of α,β-epoxy diazomethyl ketones 1a-1with activated copper powder or copper(II) sulfate in methanol (or ethanol) lead to 1,1 - dialkoxy - but - 3 - ene - 2 - ones 2 (or 3) in good yields. This process of oxygen transfer proceeds via initially generated keto-carbenoids which react intramolecularly with the epoxide function to give bicyclic intermediates 10. Release of strain and subsequent ring opening produces but - 3 - ene - 1,2 - diones which acetalise to give the ultimate reaction products 2 (or 3). With copper as catalyst byproducts were isolated, viz 1,1 - dialkoxy - 4 - hydroxy - butane - 2 - ones (4 and 5), and indanone derivative 6. An explanation for these side reactions has been given.