819871-63-1

Upstream product

• 583-55-1 1-Bromo-2-iodobenzene 
• 38274-16-7 2-bromo-1-(trimethylsilylethynyl)benzene 
• 852390-09-1 trimethyl((2-(3-methylbut-2-en-1-yl)phenyl)ethynyl)silane 

Downstream Products

• 1402404-09-4 (4S,10aS)-3-(4-methoxyphenyl)-1,1-dimethyl-4-phenyl-3,4,10,10a-tetrahydro-1H-indeno[1,2-e][1,2]oxazepine 
• 1402404-10-7 ethyl 4-((4S,10aS)-1,1-dimethyl-4-phenyl-1H-indeno[1,2-e][1,2]oxazepin-3(4H,10H,10aH)-yl)benzoate 
• 1402404-07-2 methyl 4-((4S,10aS)-1,1-dimethyl-3-phenyl-3,4,10,10a-tetrahydro-1H-indeno[1,2-e][1,2]oxazepin-4-yl)benzoate 
• 1402404-11-8 (4S,10aS)-1,1-dimethyl-4-(4-nitrophenyl)-3-phenyl-3,4,10,10a-tetrahydro-1H-indeno[1,2-e][1,2]oxazepine 
• 1402403-91-1 (4S,10aS)-1,1-dimethyl-3,4-diphenyl-3,4,10,10a-tetrahydro-1H-indeno[1,2]oxazepine 

Relevant academic research and scientific papers

Silver-Free Au(I) Catalysis Enabled by Bifunctional Urea- and Squaramide-Phosphine Ligands via H-Bonding

A library of gold(I) chloride complexes with phosphine ligands incorporating pendant (thio)urea and squaramide H-bond donors was prepared with the aim of promoting chloride abstraction from Au(I) via H-bonding. In the absence of silver additives, complexes bearing squaramides and trifluoromethylated aromatic ureas displayed good catalytic activity in the cyclization of N-propargyl benzamides, as well as in a 1,6-enyne cycloisomerization, a tandem cyclization-indole addition reaction and the hydrohydrazination of phenylacetylene. Kinetic studies and DFT calculations indicate that the energetic span of the reaction is accounted by both the chloride abstraction step, facilitated by the bidentate H-bond donor via an associative mechanism, and the subsequent cyclization step.

Enantioselective Alkoxycyclization of 1,6-Enynes with Gold(I)-Cavitands: Total Synthesis of Mafaicheenamine C

Chiral gold(I)-cavitand complexes have been developed for the enantioselective alkoxycyclization of 1,6-enynes. This enantioselective cyclization has been applied for the first total synthesis of carbazole alkaloid (+)-mafaicheenamine C and its enantiomer, establishing its configuration as R. The cavity effect was also evaluated in the cycloisomerization of dienynes. A combination of experiments and theoretical studies demonstrates that the cavity of the gold(I) complexes forces the enynes to adopt constrained conformations, which results in the high observed regio- and stereoselectivities.

Visible-Light Mediated Hydrosilylative and Hydrophosphorylative Cyclizations of Enynes and Dienes

Described herein is a visible-light mediated intermolecular radical cyclization approach to access heterocycles. Heteroatom radicals, such as silicon and phosphorus atom radicals, were generated via direct hydrogen atom abstraction by the photoexcited catalyst species with hydro-silanes and phosphine oxides. The radical addition/cyclization/HAT (hydrogen atom transfer) reaction sequences of 1,6-enynes and 1,6-dienes were highly efficient delivering the desired heterocycles in good yields.

Intermolecular gold-catalyzed diastereo- and enantioselective [2+2+3] cycloadditions of 1,6-enynes with nitrones

Going for gold: The title reaction has been developed and demonstrates a wide substrate scope with respect to the 1,6-enynes and nitrones (see scheme; DCE=1,2-dichloroethane, Tf=trifluoromethanesulfonyl). The results for the enantioselective versions are

Rutheniun-catalyzed cycloisomerization of o-(ethynyl)phenylalkenes to diene derivatives via skeletal rearrangement

Treatment of a series of 2′,2′-disubstituted (oethynyl)styrenes with TpRu(PPh3)(CH3CN)2PF6 (10 mol %) in benzene (80°C, 12-18 h) efficiently gave 2-alkenyl-1H-indene derivatives. This catalytic reaction represents an atypical enyne cycloisomerization with skeletal rearrangement of starting enyne, where the C=C bond is completely cleaved and inserted by the terminal alkynyl carbon. The reaction mechanism was elucidated by a series of deuterium and 13C labeling experiments, as well as by changing the substituents at the phenyl moieties. The mechanism is proposed to involve the following key steps: 5-endo-dig cyclization of ruthenium-vinylidene intermediate, a nonclassical ion formation, and the "methylenecyclopropane-trimethylenemethane" rearrangement.