Alkene Oxidation by a Platinum Oxo Complex and Isolation of a Platinaoxetane

Abstract

Oxo complex [(1,5-COD)4Pt4(mu3-O)2Cl2](BF4)2 (1) reacts readily with ethylene and norbornylene. The ethylene reaction yields acetaldehyde and a 1:1 mixture of (1,5-COD)Pt(Cl)(CH2CH3) (2) and [(1,5-COD)Pt4(eta3-CH2CHCH(CH3))](BF4) (3), while the norbornylene reaction yields a platinaoxetane complex, the first metallaoxetane to be obtained from the reaction of an oxo complex and an alkene.

Oxygen-17 NMR spectroscopy: Basic principles and applications (part II)

“…Sharp et al [862] investigated by 13 (Fig. 169) revealed the presence of a 17 O labelled P@O group of tppts-oxide (tpptso) at d = 49.8 ± 0.5 ppm ( 1 J(O,P) = 100 ± 20 Hz).…”

Cleavage of CS and OH Bonds by Platinum(0) Complexes To Give Five‐Membered 1,2‐Oxaplatinacycles

“…[9] As a four-membered analogue, Sharp and co-workers have reported the formation and unique reactivity of platinaoxetane 3 (cod = 1,5-cyclooctadiene). [10] Herein, we report the cleavage of C(sp 3 )ÀS and O À H bonds of 2-hydroxybenzyl sulfide derivatives 4 mediated by platinum(0). This process led to an unusual formation of novel five-membered 1,2-oxaplatinacycles (5 a, 5 b; see Scheme 2 for structures).…”

The Catalysis Gold Rush: New Claims

“…A related reaction of a platinum(ii) compound had been reported before, but there the oxygen always coordinated to two platinum centers and the formation of oxiranes was not observed. [22] While Teles et al…”

“…A related reaction of a platinum(ii) compound had been reported before, but there the oxygen always coordinated to two platinum centers and the formation of oxiranes was not observed. [22] While Teles et al [8b] initially suggested a syn oxyauration for the gold(i)catalyzed additions of alcohols to alkynes, we have proven an anti oxyauration for the gold(iii)-catalyzed oxazole synthesis. [20a] It will be a future challenge for both theoreticians and experimentalists to verify whether Cinellus synaddition mode is a general principle or the outcome of the preferred exo addition at the strained norbornene.…”