Synthesis of cyclohexadienylstannanes – Novel example of vinylic SRN1 mechanism: A theoretical and experimental study

Recent advances in the synthesis of stannanes and the scope of their posterior chemical transformations

“…This behavior is mainly due to differences in spin density of their radical anions intermediates, which affect their fragmentation rates. These results are supported by computational calculations [63].…”

Diorganostannide Dianions (R2Sn2−) as Reaction Intermediates Revisited: In Situ 119Sn NMR Studies in Liquid Ammonia

“…The in situ formation of organotin anions in liquid ammonia is a key step in the synthesis of a wide spectrum of organic tin compounds. − In this context, diorganostannides R 2 Sn 2− have been advanced as intermediates for different organometallic syntheses, including deuteration of carbonyl compounds, preparation of asymmetric stannanes, , and formation of polymers . However, conclusive spectroscopic evidence for the formation of diorganostannide dianions is not available; for instance 119 Sn-Mössbauer spectroscopy did not lead to identification of specific compounds.…”

Iron Dienylphosphate Tricarbonyl Complexes as Water-Soluble Enzyme-Triggered CO-Releasing Molecules (ET-CORMs)

“…The synthesis of cyclohexa-1,3-dien-1-yl diethyl phosphate (9) was achieved as shown in Scheme 3. In contrast to an earlier method (based on the deprotonation of nonconjugated 3cyclohexen-1-one with lithium tetramethylpiperidide (LiTMP) 13 or lithium diisopropylamide (LDA) 14 and subsequent reaction with diethyl chlorophosphate), we succeeded in regioselectively generating the required dienolate starting from 2-cyclohexen-1-one ( 8) by deprotonation with lithium hexamethyldisilazide (LiHMDS) in the presence of tripyrrolidinophosphoric acid triamide (TPPA) as a cosolvent. Complexation of the dienylphosphate 9 under established conditions ((η 4 -benzylideneacetone)Fe(CO) 3 in toluene) 12 yielded the desired complex rac-6a in good overall yield (Scheme 3).…”