An intriguing stepwise diradical mechanism of the dimerization of the reactive intermediate (thiocarbonyl S-methanide) appearing in the reaction of phenyl selenophen-2-yl thioketone with diazomethane was studied by means of computational methods. The preferred formation of the unusual macroheterocycle, competitive with the 1,3-ring closure leading to a thiirane and the head-to-head dimerization...

+ [21]. 68 [23]. ALGOL [10, 15, 17, 18, 21, 23, 5, 20]. Algol-based [20]. ALGOL-N [21]. based [20]. Bulletin [24, 5, 10, 15, 17, 18, 12, 14, 4, 7, 11, 3, 6, 9, 16]. collateral [20]. considered [1]. defining [20]. execution [20]. FORTRAN [14, 12]. general [20]. generation [23]. Go [1, 2]. harmful [1]. hybrid [20]. infinite [22, 23]. information [12, 14, 4]. involving [23]. Jovial [4]. language [...

The design, synthesis, and validation of a new bifunctional aldehyde linchpin for Type II anion relay chemistry have been achieved. For this linchpin, the initial nucleophilic addition proceeds under Felkin-Anh control to generate the syn-alkoxide, which undergoes a 1,4-Brook rearrangement to relay the negative charge, thus leading to the formation of a dithiane-stabilized carbanion. Subsequent...

1,3-dithianyl cation radicals having alpha-hydroxy-neopentyl or similar groups in position 2, which are generated via oxidative photoinduced electron transfer, undergo anomalous fragmentation necessitating refinement of the accepted mechanism. Experimental and computational data support a rationale in which proton abstraction from the hydroxy group in the initial cation radical does not cause a...