Other Unsaturated Alcohols

Imamoto, Y. Hatanaka, Y. Tawarayama, and M. Yokoyama, Tetrahedron Lett., 1981, 22,4987. 

lijima, H. Moriya, and M. Sato, J. Chem. Soc., Chem. Commun., 1981, 1140. 

spectroscopic method has been reported for determination of the stereochemistry of 1,2-diols by examination of the trans-N,N,N, N -tetramethylcyclohexane-l,2-diamine complexes of their cyclic osmate-(vi)esters. Organic selenoxides such as PhiSeO have been introduced as new 

Reagents i, PhSH-HBp4 ii, potassium naphthalenide iii, ClB(NMe2)2 iv, Me2C(OH)C(OH)Me2 V, RCHO vi. N(CH2CH20H)3 vii. Bu Li—TMEDA 

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This preparation illustrates a general and convenient way of oxidizing secondary alcohols to ketones. The novel feature of the reaction is represented by acetone solvent which affects markedly the properties of the oxidizing agent. The reaction is very rapid (if not instantaneous), and the yields are high, the reagent rarely attacking unsaturated centers. The procedure is applicable to acetylenic carbinols, allyl and other unsaturated alcohols, and saturated carbinols. The main limitation is the low solvent power of acetone. 

In addition to allylic alcohols, other unsaturated alcohols react with halides to give carbonyl compounds. Although the reaction was slow (three days), the reaction of 10-undecen-l-ol (50) with iodobenzene afforded the aldehyde 52 in a high yield. In this... 

Substituted olefins also complex with CuCl. The halide dissolves in allyl alcohol owing to complex formation 183, 184). Other unsaturated alcohols give complexes of the type (alkenol)CuCl and [(alkenol)Cu] + when added to solutions of CuCl in aqueous HCl 185). Similar complexes are formed with various unsaturated carboxylic acids, and the stability of the complexes is influenced by the stereochemistry about the double bond 13). Maleic acid, however, forms the anionic complex [CuCl(02C -CH=CH.C02H)] in addition to the neutral and cationic complexes 11, 12). 

In allylic and other unsaturated alcohols, formation of an 0-H insertion product clearly dominates the cyclopropanation reaction,e.g. formation of 18 and 19. 

Other Unsaturated Alcohols. Hydroboration with 9-BBN occurs at the less substituted end of unsymmetrical allenes (illustrated in Scheme 19 for a terminal allene) to give exclusively allylboranes (43). In combination with the known... 

Other Unsaturated Alcohols. The review mentioned above of carbometallation of alkynes, includes a survey of additions of alkenyl-metal derivatives to epoxides to give homoallylic alcohols. The zirconium-catalysed carboalumination of propargylic systems (Scheme 16) is also applicable to the homopropargylic to homoallylic alcohol transformation. ... 

Other Unsaturated Alcohols. Dimethylaluminium chloride has been found to be a useful catalyst for the ene reaction of aliphatic and aromatic aldehydes with alkenes (Scheme 16) to produce homoallylic alcohols/ by acting as a mild Lewis acid and proton scavenger rapid decomposition of the product alcohol-Lewis acid complex (42), a strong proton acid species, gives methane and a non-acidic alkoxide, thus avoiding protonation of the carbon-carbon double bond in the alkene or ene adduct, 1,1-Disubstituted alkenes are the most reactive under these conditions, and the yields of ene additions to formaldehyde are also improved. 

Other Unsaturated Alcohols. An improved procedure that has been reported recently for the preparation and utilization of alkali-metal acetylides in liquid ammonia allows the ethynation of sensitive carbonyl compounds to be carried out, in good yield, to give propargylic alcohols. The reduction of ap-acetylenic ketones to (S propargyl alcohols of high enantiomeric purity can be performed with NB-Enantrane (27) [cf. (6) earlier], which is derived from nopol benzyl ether as a low-cost alternative to (—)-a-pinene. a-Allenic alcohols have been prepared by the new routes shown in Schemes... 

Other Unsaturated Alcohols, y,5-Unsaturated (homoallylic) alcohols may be made by homologation of allyl alcohols with allylic transposition using a new method that involves [2,3] sigmatropic rearrangement of an a-allyloxy-organolithium (34) (Scheme 17) some comments on the observed stereochemistry have been made. 

Carbonyl Group Reduction Allylic Alcohols Other Unsaturated Alcohols Reactions Protection 1,2-Diols... 

L. is a fatty alcohol derived from linoleic acid. It is normally contained in a mixture with other unsaturated alcohols (broad cut). Production and uses are the same as - linolenyl alcohol. 

The reaction of ozone with allyl alcohol is expected to involve, as for other unsaturated alcohols and olefins, electrophilic addition at the carbon-carbon double bond leading to the formation of a trioxide followed by its unimolecular decomposition into two carbonyls and two biradicals (Criegee intermediates) ... 

The reaction of NO3 with a 5 -2-penten-l-ol may lead to the formation of a series of aldehydes, such as formaldehyde, acetaldehyde, propanal, and glycolaldehyde. The reaction may also produce nitrooxy-aldehydes similarly to that observed for other unsaturated alcohols (Noda et al., 2000). 

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