Solvent- and Metal-Controlled Regiodivergent Synthesis of Tri­fluoromethylated Pyrazol-3-yl- and Pyrazol-5-ylphosphonates

Abstract

Convenient approaches to the selective syntheses of trifluoromethylated pyrazol-3-yl- and pyrazol-5-ylphosphonates have been developed based on solvent- and metal-controlled reaction of diethyl (4,4,4-trifluoro-3-oxobut-1-yn-1-yl)phosphonate and monosubstituted hydrazines.

Regiodivergent Metal-Controlled Synthesis of Multiply Substituted Quinolin-2-yl- and Quinolin-3-ylphosphonates

“…In particular, they are used in synthesis of acyl-substituted quinolines, but such syntheses are limited to a few examples . In this class, phosphoryl-substituted conjugated ynones of the (3-oxoprop-1-yn-1-yl)­phosphonates series are of interest . Earlier we developed methods for synthesis of these compounds and demonstrated their application in synthesis of pyrazolylphosphonates. , …”

Divergent Synthesis of (Benzo[b][1,4]diazepin‐2‐yl)phosphonates and (Quinoxalin‐2‐yl)methylphosphonates from Phosphoryl‐Substituted Conjugated Ynones

“…Conjugated ynones are very valuable and widely used reagents in synthesis of various heterocyclic compounds [2] and in turn phosphorylated ynones are convenient building blocks for preparation of phosphorylated heterocycles [3] . Their ability to react with nucleophiles, giving the product of 1,2‐ or 1,4‐ addition, can be used to obtain both regioisomers, that we used earlier in the synthesis of regioisomeric pyrazoles [4] . Moreover, in the case of alkynes bearing two electron acceptor groups of different nature (acyl and phosphoryl), it is possible to control selectivity of nucleophilic addition on the triple bond.…”