Heterophospholes

Enantiomerically Pure N Chirally Substituted 1,3-Benzazaphospholes: Synthesis, Reactivity toward tBuLi, and Conversion to Functionalized Benzazaphospholes and Catalytically Useful Dihydrobenzazaphospholes

“…The chiral benzazaphosphole 4b (Figure ) displays the expected planarity of the fused ring system (mean deviation 0.005 Å) with C8 lying 0.12 Å out of the plane. The N–C2 and P–C2 bonds are short in comparison to the N–C7A and P–C3A bonds, as is typical for 1,3-benzazaphospholes . With respect to 1-neopentyl-1,3-benzazaphosphole, bearing a moderately bulky primary N-alkyl group, the P–C2 (double) bond is perhaps marginally longer (by 0.0087(14) Å), but N–C2 and the other bonds of the ring system are very similar.…”

“…1,3-Benzazaphospholes , constitute a special type of trivalent phosphorus compound. Like the more familiar phosphabenzenes (phosphinines), they exhibit dicoordinated phosphorus and aromatic stabilization, but the presence of the nitrogen electron lone-pair in a position β to phosphorus, supported by the inductive electron-withdrawing effect of nitrogen, induces increased π density in the ring and at phosphorus and changes the reactivity.…”

Unexpected Thermal Reactivity of Phosphirano‐[1,2]thiaphosphole P–W(CO)5 Complexes

“…[21] We found that 11a could be desulfurated with tributylphosphane within 1 min to furnish the W(CO) 5 -containing complex 13 quantitatively (Scheme 7). Owing to its high sensitivity toward oxygen (see below), this phosphole, which displays a 31 P NMR resonance (δ P = 233.5 ppm) in the expected [22] range, could not be separated from the byproducts. When polymer-supScheme 7.…”

A New Concept for the Efficient Synthesis of Chiral Phosphorus−Nitrogen−Carbon Cage Compounds

“…The almost planar 2H-1,2-azaphosphole ring of complex 11 (mean deviation of 0.02 Å ) showed no unusual atom dis-tances when compared to complex 14 (Figure 2), [15] the only known structure of a P-Cp*-substituted phosphole [27,28] or heterophosphole. [29] As a common structural motif in diester-substituted 2H-1,2-azaphosphole rings [25] the ester group at C16 almost shows an in-plane orientation, whereas the ester group at C-17 is oriented out-of-plane. The torsion angle of N(1)ϪC (18)ϪN (2)ϪP (2) is 0.3°and, therefore, should enable electronic interactions between the substituent and the ring system.…”