Chemistry of selected cyclic P(III) compounds possessing a P-Cl bond

Abstract

The compounds [CH 2 (6-t-Bu-4-Me-C 6 H 2 O) 2 ]PCl (1), (OCH 2 CMe 2 CH 2 O)-PCl (2), and [ClPN(t-Bu)] 2 (3) have been utilized as precursors in the synthesis of (i) new pentacoordinate phosphorus compounds [e.g. CH 2 (6-t-Bu-4-Me-C 6 H 2 O) 2 P(NRR′)(O 2 C 6 Cl 4), CH 2 (6-t-Bu-4-Me-C 6 H 2 O) 2 PX[OC(O-i-Pr)N=N(C(O)O-i-Pr)], (ii) cyclic phosphates and their complexes [e.g. {imidazolium} + {CH 2 (6-t-Bu-4-Me-C 6 H 2 O) 2 PO 2 }-.MeOH], (iii) new cycloaddition products [e.g. {CH 2 (6-t-Bu-4-Me-C 6 H 2 O) 2 }P{C(CO 2 Me)C(CO 2 Me)C(O)N}, (iv) macrocyclic compounds [e.g. {[(t-BuN)P] 2 [-OCH 2 CMe 2 CH 2 O-]} 2 ] and (v) phosphonates [e.g. (OCH 2 CMe 2 CH 2 O)P (O)CH 2 C(CN)=CHC 5 H 4 FeC 5 H 5 ]. The synthetic and structural aspects of these new products are discussed.

Functionalized phosphorus derivatives of Salpen-like compounds: Synthesis and preliminary complexation studies

“…For instance, both steps can be inverted, as shown by the condensation of 1 with 3d leading to the azide 5d (Scheme 2). In view of the small number of compounds possessing a k 4 ,r 5 -phosphorus azide linkage characterized by X-ray diffraction (only five examples) [14][15][16][17][18], it appeared interesting to obtain single crystals of 5d. The ORTEP drawing of 5d is shown in Fig.…”

Exploring organic reactions using simple cyclodiphosphazanes

“…The primary intermediates in these reactions are the phosphonium salts (betaines) depicted as [(MeO 2 C)C À @C(CO 2 Me)-PR þ 3 ] (1), [R 0 (O)C-C(H) À C(@CH 2 )-PR þ 3 ] (2), [R 0 (O)C-C(H)@C(CH 2 ) À -PR þ 3 ] (3) and [(EWG)CH À -CH 2 -PR þ 3 ] (4) EWG@CN, CO 2 R) in Scheme 1 [5]. It must be noted that if the phosphorus(III) compound bears functionalities like -NCO, -NCS or -N 3 , the reaction with activated alkynes would involve these groups also [6]. One of the most important reactions among those shown in Scheme 1 is the Morita-Baylis-Hillman reaction [7] that leads to a diverse number of functionalized and synthetically useful allylic systems.…”

“…We have also explored the reaction of allenylphosphonates with the cyclodiphosphazane [(t-BuNH)P(l-N-t-Bu)] 2 (6). Interestingly, we could isolate both the enantiomers of the product [(t-Bu-NH)P(l-N-t-Bu) 2 P(@N-t-Bu)C(@CH 2 )-CH(Ph)-P(O)(OCH 2 CMe 2 CH 2 O)] (16) from the reaction of 6 with the allene (OCH 2 CMe 2 CH 2 O)P(O)C(Ph)@C@CH 2 (15) [10].…”

“…In the course of our studies on cyclophosphazanes we have also made some new observations related to molecular non-stoichiometry that involves lone pair/phosphoryl bonds in cyclodiphosphazanes. In addition to giving a brief review of our work in this paper, we present the X-ray structures of the new compounds [(tBuNH)(PhCH 2 CH(CN)CH 2 -)P(l-N-t-Bu) 2 P(NH-t-Bu)] + [HCO 3 ] À (13), [(t-BuNH)P(l-N-t-Bu) 2 P(@N-t-Bu)-C(@CH 2 )CH(C 6 …”

The first structural study on a cyclic tricoordinate phosphorochloridite and a pentacoordinate phosphorane based on 1,2,3,5-protected myo-inositol—a new conformation of 1,3,2-dioxaphosphorinane ring

“…Its 31 P NMR spectrum shows a peak at d À53.1 consistent with pentacoordination in soln. 13,19,20,[27][28][29][30][31][32] The molecular structure of 9AECH 2 Cl 2 along with the bond parameters is shown in Figure 2. The more electronegative oxygen atoms occupy the apical positions while the less electronegative nitrogen is equatorial in the trigonal bipyramidal (TBP) structure, as expected from Bent's rule.…”