Concise Seven-Membered Oxepene/Oxepane Synthesis – Structural Motifs in Natural and Synthetic Products

This work outlines a suitable method for the synthesis of oxepane skeleton using iterative C-glycoside technology on the oxepene intermediate, which was synthesized utilizing Wilkinson’s catalyst [Rh(PPh3)3Cl] to generate the isomerized product in a linear synthetic manner. The central core of the oxepene motif was achieved via an olefin metathesis reaction using the Grubbs second-generation and Schrock catalysts. The synthesis of the functionalized oxepane having the desired adriatoxin E-ring relative stereochemistry was achieved starting from commercially available homopropargylic alcohol.

Non-metal-templated approaches to bis(borane) derivatives of macrocyclic dibridgehead diphosphines via alkene metathesis

Two routes to the title compounds are evaluated. First, a ca. 0.01 M CH2Cl2 solution of H3B·P((CH2)6CH=CH2)3 (1·BH3) is treated with 5 mol % of Grubbs' first generation catalyst (0 °C to reflux), followed by H2 (5 bar) and Wilkinson's catalyst (55 °C). Column chromatography affords H3B·P(n-C8H17)3 (1%), H3B· P ((CH2)13 C H2)(n-C8H17) (8%; see text for tie bars that indicate additional phosphorus–carbon linkages, which are coded in the abstract with italics), H3B· P ((CH2)13 C H2)((CH2)14) P ((CH2)13 C H2)·BH3 (6·2BH3, 10%), in,out-H3B·P((CH2)14)3P·BH3 (in,out-2·2BH3, 4%) and the stereoisomer (in,in/out,out)-2·2BH3 (2%). Four of these structures are verified by independent syntheses. Second, 1,14-tetradecanedioic acid is converted (reduction, bromination, Arbuzov reaction, LiAlH4) to H2P((CH2)14)PH2 (10; 76% overall yield). The reaction with H3B·SMe2 gives 10·2BH3, which is treated with n-BuLi (4.4 equiv) and Br(CH2)6CH=CH2 (4.0 equiv) to afford the tetraalkenyl precursor (H2C=CH(CH2)6)2(H3B)P((CH2)14)P(BH3)((CH2)6CH=CH2)2 (11·2BH3; 18%). Alternative approaches to 11·2BH3 (e.g., via 11) were unsuccessful. An analogous metathesis/hydrogenation/chromatography sequence with 11·2BH3 (0.0010 M in CH2Cl2) gives 6·2BH3 (5%), in,out-2·2BH3 (6%), and (in,in/out,out)-2·2BH3 (7%). Despite the doubled yield of 2·2BH3, the longer synthesis of 11·2BH3 vs 1·BH3 renders the two routes a toss-up; neither compares favorably with precious metal templated syntheses.

Mechanochemical dehydrocoupling of dimethylamine borane and hydrogenation reactions using Wilkinson's catalyst

Synthesis and use of the emblematic Wilkinson's catalyst by mechanochemistry was achieved.

Reactions of Trivalent Iodine Reagents with Classic Iridium and Rhodium Complexes

In this work, the reactions of iodine(iii) reagents (PhI(L)2: L = pyridine, acetate (OAc−), triflate (OTf−)) with iridium(i) and rhodium(i) complexes (Vaskas’s compound, Wilkinson’s catalyst, and bis[bis(diphenylphosphino)ethane]rhodium(i) triflate) are reported. In all cases, the reactions resulted in two-electron oxidation of the metal complexes. Mixtures of products were observed in the reactions of Iiii reagents with Vaska’s compound and Wilkinson’s catalyst via ligand exchange and anion scrambling. In the case of reacting Iiii reagents with chelating ligand-containing bis[bis(diphenylphosphino)ethane]rhodium(i) triflate, no scrambling was observed.