Synthesis of methyl-substituted trans- and cis-1-thiadecalins

Indium Triflate‐Catalysed Addition of Thio Compounds to Camphene: A Novel Route to 2,3,3‐Trimethyl‐2‐thiobicyclo[2.2.1]heptane Derivatives

“…Besides the addition to camphene, In(OTf) 3 was also an efficient catalyst for the addition of sulfur nucleophiles to olefins.…”

“…At higher temperatures, high regioselectivities towards the isomerised isobornyl thio-functionalised structures 2 were obtained. The access to new compounds, the use of a catalytic amount of In(OTf) 3 under mild conditions, without the need for an additional ligand, and the potential to recover and recycle the catalyst [20] constitute further advantages of this new catalytic reaction.…”

“…General Procedure: The thioacid or the thiol (5 mmol) was added to a mixture of camphene 1 (5 mmol), and In(OTf) 3 (0.25 mmol) in dichloroethane (5 mL) and the mixture was stirred at the desired temperature. The progress of the reaction was monitored by GC analysis.…”

“…[1] Generally, this reaction proceeds through a radical-type mechanism with initiators, such as peroxides, AIBN or photochemistry, resulting in the addition of thio derivatives to the double bond with antiMarkovnikov regioselectivity. [2,3] Electrophilic-type additions with strong protic [4][5][6] or Lewis [7,8] acids in over-stoichiometric amounts result in the formation of Markovnikov-type adducts with some olefin polymerisation. We recently reported on the catalytic and efficient use of "super" Lewis acids derived from triflates for the selective functionalisation of nonactivated olefins in hydroalkoxylation cycloisomerisations and hydrothiolations.…”

Preparation of Sixteen 3‐Hydroxy‐4‐ and 7‐Hydroxy‐1‐hydrindanones and 3‐Hydroxy‐4‐ and 8‐Hydroxy‐1‐hydroazulenones

“…3‐Cyclohex‐2‐en‐1‐ylpropan‐1‐ol (13f): 22 As described in a previously published procedure,9a p ‐tosylhydrazone 13e (4.25 g, 11.6 mmol), MeLi (1.6 M in ether, 50 mL, 80 mmol), and TMEDA (20 mL) in dry THF (120 mL) afforded, after 23 h at room temp., the known22 alkenol 13f , which was purified on a column B ( x / y = 10:1), to give 1.61 g (99 %). 1 H NMR: δ = 1.16–1.86 (m, 9 H), 1.93–2.14 (m, 3 H), 3.64 (t, J = 6.6 Hz, 2 H), 5.57 (m, 1 H), 5.67 (m, 1 H) ppm.…”