Efficient Syntheses of (α-Fluoropropargyl)phosphonate Esters

Introduction of Fluorine and Fluorine‐Containing Functional Groups

“…The synthesis of propargylic fluorides can be accomplished by the deoxyfluorination of propargylic alcohols with DAST146 or fluorination of a variety of activated propargylic substrates147 such as propargylic mesylates or silyl ethers. Other commonly used deoxofluorinating reagents for the synthesis of propargylic fluorides include SF 4 ,147a,b, 148 dialkylaminosulfur trifluorides,147c,d,f,g Yarovenko’s reagent (Figure 2),149 and Ghosez’s reagent ( N , N ‐diisopropyl‐1‐fluoro‐2‐methylpropenamine) 150. Grée and co‐workers achieved the synthesis of chiral propargylic fluorides through an S N 2 reaction between chiral, nonracemic propargylic alcohols and fluoride 151.…”

Nonenzymatic kinetic resolution of racemic β-hydroxyalkanephosphonates with a chiral copper catalyst

“…On the other hand, p-TsCl and ClP(O)(OEt) 2 did not react with (Entries 18 and 19). MeCN 24 32 68 17 2 6 DMF 0 ->99 --7 DMSO 0 ->99 --8 acetone 14 19 71 13 2 13 benzene 22 59 75 24 5 14 toluene 30 34 70 24 3 15 mesitylene 12 61 75 22 5 16 CH 2 Cl 2 32 80 66 28 12 17 CHCl 3 25 72 57 22 8 18 CCl 4 20 60 77 23 [4][5][6][7][8][9]. On the other hand, diisopropylethylamine (DIPEA) gave (S)-2a(2-FBz) with low yield and selectivity (Entry 10).…”

The α-hydroxyphosphonate-phosphate rearrangement of a noncyclic substrate – some new observations

“…This isomerisation discovered for X = O by Sturtz and Corbel 2 is called phosphate-phosphonate or more specifically phosphate-α-hydroxyphosphonate rearrangement. This [3][4][5] and the versions for X = S 6,7 and N 8 have extensively been studied by Hammerschmidt's group. The reverse process with many examples 9-17 for X = O, the α-hydroxyphosphonate-phosphate rearrangement, also termed [1,2]-phospha-Brook rearrangement, has been found by Pudovik and Konovalova 17 before the phosphate-phosphonate rearrangement.…”