55282-88-7Relevant academic research and scientific papers
Bis(imino)pyridine iron complexes for aldehyde and ketone hydrosilylation
Tondreau, Aaron M.,Lobkovsky, Emil,Chirik, Paul J.
supporting information; experimental part, p. 2789 - 2792 (2009/05/27)
(Chemical Equation Presented) Bis(imino)pyridine iron dinitrogen and dialkyl complexes are well-defined precatalysts for the chemo- and regioselective reduction of aldehydes and ketones. Efficient carbonyl hydrosilylation is observed at low (0.1-1.0 mol %) catalyst loadings and with 2 equiv of either PhSiH3 or Ph2SiH2, representing one of the most active iron-catalyzed carbonyl reductions reported to date.
Mitsunobu Reaction of Unbiased Cyclic Allylic Alcohols
Shull, Brian K.,Sakai, Takashi,Nichols, Jeffrey B.,Koreeda, Masato
, p. 8294 - 8303 (2007/10/03)
The stereochemical inversion of unbiased allylic alcohols using triphenylphosphine, diethyl azodicarboxylate, and benzoic acid, commonly known as the Mitsunobu reaction, was studied in three different solvents with specific attention toward the product composition. The results generated for the Mitsunobu reaction of (R)-3-deuterio-2-cyclohexen-1-ol and the cis and trans isomers of 1-deuterio-5-methyl-2-cyclohexen-1-ol, 1-deuterio-5-tert-butyl-2-cyclohexen-1-ol, and optically active cis and trans 5-isopropyl-2-methyl-2-cyclohexen-1-ol all gave similar product distributions with respect to inversion and retention at the carbinol center as well-as syn and anti Sn2′ type addition when THF or benzene was used as the solvent (CH2Cl2 gave less selective product distributions). Interestingly, it was found that the quasi-equatorial and quasi-axial nature of the starting allylic alcohol does not appear to affect the product distribution for this reaction, nor does methyl substitution at the central carbon of the allylic alcohol. In all cases, significant amounts (8-28%) of non-SN2 type products were detected for these sterically unbiased allylic alcohols; only 72-77% of the product was from SN2 type reaction when sterically undemanding (R)-S-deuterio-2-cyclohexen-1-ol was subjected to Mitsunobu conditions.
The mechanism of oxidation of allylic alcohols to α,β-unsaturated ketones by cytochrome P450 a
Bellucci, Giuseppe,Chiappe, Cinzia,Pucci, Laura,Gervasi, Pier Giovanni
, p. 871 - 874 (2007/10/03)
The oxidation of cyclohex-2-en-1-ol, a simple model substrate for allylic alcohols, is catalyzed by several P450 isoenzymes and leads exclusively to cyclohex-2-en-1-one. No double bond epoxidation or C(4) hydroxylation have been observed. The large primary kinetic isotope effect measured using [2H]-1-cyclohex-2-en-1-ol is consistent with an at least partially rate limiting breaking of the C(1)-H bond. The mass spectrometric analysis of cyclohex-2-en-1-one obtained from [18O]cyclohex-2-en-1-ol has established that a gem-diol intermediate is involved, even if a dual hydrogen abstraction pathway may contribute to the reaction.
On the Solvolysis of 2-Cyclohexenyl 3,5-Dinitronbenzoate and p-Nitrobenzoate in Aqueous Acetone. Introduction of Acyl-Oxygen Cleavage by Basic Buffer Systems
Kantner, Steven S.,Humski, Kresimir,Goering, Harlan L.
, p. 1693 - 1697 (2007/10/02)
Solvolysis of α- and β-deuterium-labeled 2-cyclohexenyl 3,5-dinitrobenzoate (1-ODNB) and p-nitrobenzoate (1-OPNB) in 60percent aqueous acetone containing diisopropylethylamine (to protect initially formed product from subsequent acid-catalyzed allylic rea
