From unsaturated alcohols

A regio- and stereospecific INOC reaction of unsymmetrical silaketals 114, synthesized in one pot from unsaturated alcohols, nitro ethanol, and dichloro-silanes, via the nitrile oxide 115 to isoxazolines 116 has been described (Scheme 14) [37a]. The intermolecular version of the cycloaddition, under similar conditions, proceeds with poor regio and stereoselectivity. 

The synthesis of tetrahydrofuran derivatives from unsaturated alcohols via hydroformylation intermediates was developed many years ago. Moderate yields are obtained from but-2-en-l,4-diol (Scheme 54)94 but hydroformylation is not the major pathway when coniferyl alcohol is subjected to the oxo process (Scheme 55).9S A more complicated reaction is involved... 

There have been very few reports of alkoxy complexes derived from unsaturated alcohols. A vinoxytitanium derivative can be obtained from the reaction of tetraisopropoxytitanium and acetaldehyde (equation 15).68 More recently, the dimer [Ti(OCH2CHCH2)4]2 has been isolated from reaction (16).69... 

A very few examples of the use of aryl-tin,21 -lead,21 -lithium43 and -magnesium21143,44 derivatives as the source of the aryl group in vinyl substitutions have been reported. Tin derivatives have been used with palladium dichloride bis(benzonitrile) and a copper(II) chloride reoxidant in a regioselective synthesis of oxygen heterocycles from unsaturated alcohols.43... 

Whittaker and co-workers805,806 have also prepared a number of terpenoid bicyclic ethers, such as isomeric 1,6-dihydrocarveols 199 (HSO3F—S02,78°C) from unsaturated alcohols or diols.805 806pura-Menth-l-en-9-ol and a related diol afforded the seven-membered ring systems 200. The oxolane moiety in compound 201 was generated from the corresponding unsaturated alcohol precursor in 2 equivalents of triflic acid.807... 

Synthesis of y-lactones from unsaturated alcohols and CO catalyzed by Pd complexes 91YGK909. 

Some examples of diazoacetic esters bearing functionalized ester groups are given in Table 12. For intramolecular cyclopropanation reactions with diazoacetic esters derived from unsaturated alcohols see Section 1.2.1.2.4.2.6.3.4. 

Octene and 1-undecene are converted to internal olefins by illumination in the presence of Fe(CO)s or Fe3(CO)i2 20>21>91) in an intramolecular reaction 149>. Cic/trans isomerization of 1.6-cyclodecadiene has been reported 222> (illumination with Fe(CO)g). Shift of the double bond in allyl ethers to the corresponding propenyl ethers 251> or isomerization of unsaturated ethers 126> can be photoinitiated in the presence of Fe(CO)s, under similar conditions ketones and aldehydes can be prepared from unsaturated alcohols 127>. 

Cyclizathn reactions. 4-Chlorotetrahydropyrans and -thiopyrans are formed from unsaturated alcohols and thiols on condensation with carbonyl compounds, which patterns after the Prins reaction. Chlorinated oxepanes are similarly accessible. ... 

Cyclizations. A stereocontrolled synthesis of trisubstituted tetrahydropyrans by condensation of homoallylic alcohols with aldehydes is developed. Treatment of THP ethers derived from unsaturated alcohols with triflic acid leads to oxygen heterocycles. ... 

Henkel Kgaa, Preparation of Epoxidized Fatty Alcohol from Unsaturated Alcohol by Reaction with Aqueous Solutions of Hydrogen Peroxide and Formic Acid in Presence of Buffer, Without Catalyst, EP Patent 286937 (1988). 

Muzart, J. (2005) Palladium-catalysed reactions of alcohols. Part B formation of C-C and C-N bonds from unsaturated alcohols. Tetrahedron, 61, 4179-212. 

Esters made from unsaturated alcohols usually react smoothly with synthesis gas vinyl acetate gave 30% a-acetoxypropionaldehyde together with 22% of the p-isomer [24], and allyl acetate produced a-acetoxy-butyr-aldehyde in 75% yield [24]. Under certain conditions, it is possible to split out the acid group and obtain the unsaturated aldehyde [272]. 

Higher yields of lactones are obtained under usual conditions from unsaturated alcohols that cannot undergo isomerizations of this type owing to the presence of substituents in position 2. 

By judicial characterization of the kinetics of the different intermediates and products in the reactions of different substrates and by comparing the results form alcohols and acetates, the mechanism for the formation of a series of terpenes from unsaturated alcohols in the presence of the hexamers of 6e was elucidated [54c]. For example. Fig. 31.12b shows the kinetics of one of the reactions performed in the presence of [6e6(H20)g]. This analysis showed that direct rotation of the transoid allylic cation to a cisoid cation, previously thought to be impossible, does occur [54c, d]. In this study it was shown that the hexameric capsule can encapsulate the terpene, stabilize the formed carbocations in a lipophilic environment (like in an enzyme pocket) which presumably increase their lifetimes (excluding water and... 

One of the most recent developments in the field is the use of the self-assembled hexameric resorcin[4]arene capsules as reaction vessels or nano-reactors where new chemistry and catalysis may occurs. There are only few such examples however in the past year or so several convincing and interesting examples were reported. The most interesting to date is the terpenes synthesis from unsaturated alcohols, which seems to mimic the action of cyclase enzymes. Clearly there is more chemistry to discover with these nano-vessels. 

TRIORGANOTIN ALKOXIDES DERIVED FROM UNSATURATED ALCOHOLS... 

Table 17. Triorgaxiotin Alkoxides Derived From Unsaturated Alcohols... 

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