Untitled

Intramolecular cyclization of ω‐haloalkylsubstituted thiophosphorylacetonitriles: Synthesis and stereochemistry of 3‐cyano‐2‐oxo‐1,2‐thiaphosphacyclanes

“…Such similarity of thiaphosphinanium salts and cyanosubstituted cycles 14 and 15 means that the phosphorus atom in the latter compounds is characterized by a significant fractional positive charge, mainly due to the electronwithdrawing effect of both the CN group and the phosphoryl oxygen. The same conclusion can be made on the base of comparison of the P-S bond lengths in the nonfunctionalized 2-oxo-2-phenyl-1,2-thiaphosphinane [29] and 15d(A) (Figure 5), where the P-S bond length is shortened by 0.02Å, while the P(1)-C(1) bond is elongated by 0.04Å due to the presence of the CN group (Table 7). Thus, one can conclude that, for the P-S bond, the presence of electronwithdrawing substituents leads not to an elongation 15a(B), 15c(A), 15i(B), and G is the same as for all other six-membered cycles in Figures 2-6.…”

“…Thus, one can conclude that, for the P-S bond, the presence of electronwithdrawing substituents leads not to an elongation 15a(B), 15c(A), 15i(B), and G is the same as for all other six-membered cycles in Figures 2-6. b For 15h(B) the bond lengths and angles are presented only for the molecule with the occupancy 0.80. c G presents 2-oxo-2-phenyl-1,2-thiaphosphinane [29]. d For molecules 14c(B) and 15d(A) bond lengths and angles are indicated for two independent molecules.…”

Synthesis, some properties and structural features of 1,2-thiaphosphacyclanes

“…The mechanism of the reaction was established quite reliably as the authors succeeded in isolating the intermediate quasiphosphonium salt bearing the ethoxy group starting from compound (EtO)EtP(S)(CH 2 ) 3 Cl if the nucleophilic chloride anion is replaced by the perchlorate anion. 84,85 It should be noted that this is the first case where the intermediate product of the thione ± thiol rearrangement of a phosphorus thioacid ester was isolated as an individual compound. Thus, intramolecular S-alkylation represents a general method for the preparation of thiaphosphacyclanes.…”

“…The same regularity is observed when comparing the bond lengths in salts 103b (Hal = I, Br) with those in 2-oxo-1,2l 5 -thiaphosphinane 112b (R = Ph). 84 The introduction of the cyano group in position 3 of the 2-oxo-1,2-thiaphosphinane ring 86,88,89 resulted in the contraction of the P7S bonds (cf. structures 112b and 116b with different substituents R 1 and R 3 , Table 2).…”

A convenient one‐pot synthesis of 1,2‐azaphospholanium salts

“…Previously we have developed [5][6][7] a general approach to 1,2-heteraphosphacyclanes by intramolecular alkylation of -haloalkyl-substituted compounds of tetracoordinate phosphorus with P E bond 2 ( E = S, NR ). On the basis of this method, a number of N-arylsubstituted 1,2-azaphospholanium and 1,2-azaphosphinanium salts 1 (n = 3, 4) were obtained.…”