32591-15-4Relevant articles and documents
Ammonium-directed dihydroxylation of 3-aminocyclohex-1-enes: Development of a metal-free dihydroxylation protocol
Aciro, Caroline,Claridge, Timothy D. W.,Davies, Stephen G.,Roberts, Paul M.,Russell, Angela J.,Thomson, James E.
supporting information; experimental part, p. 3751 - 3761 (2009/02/04)
Treatment of 3-aminocyclohex-1-enes with mCPBA in the presence of trichloroacetic acid gives the corresponding 1,2-anti-2,3-syn-1- trichloroacetoxy-2-hydroxy-3-aminocyclohexane with high levels of diastereoselectivity (90% de). This is consistent with a mechanism of oxidation involving hydrogen-bonded delivery of the oxidant by the allylic ammonium ion formed in situ, followed by highly regioselective ring-opening of the intermediate epoxide by trichloroacetic acid. The effect of conformational constraints upon the oxidation reaction is also examined. The Royal Society of Chemistry 2008.
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 enigmatic 1J(CH) coupling constants of allyl-type organometallic compounds
Schlosser, Manfred,Lehmann, Ruth,Jenny, Titus
, p. 149 - 157 (2007/10/02)
A new attempt has been made to identify the factors responsible for the abnormally small one-bond C, H coupling constants observed for allyl, pentadienyl and heptatrienylmetal compounds.In-plane deformations (widening of the central CCC angle) should have