Ally 1 alcohol

AllyHc alkylation o( ally alcohols m the presence of copper Iodide and phosphmimines... 

A. 2,2-Dimethyl-4-pentenal. In a SOO-mL, one-necked, round-bottomed flask which contains a magnetic stirring bar are placed 108 g (1.5 mol) of 1 sobutyraldehyde (Note 1), 58 g (1.0 mol) of ally alcohol (Note 1), 230 ml of p-cymene (Note 1), and 0.4 g (2 mnol) of p-toluenesulfonic acid nonohydrate... 

Notes, fa) Rate of metallation with t-BuLi varies from case to case. Lithiation of ally] alcohol trimethylsilyl ether proceeds to completion in 2 h at -78 °C, whereas the corresponding methallyl derivative requires 3.5 h at -33°C. 

Treatment of the 1,2-oxazines 52 with carbon monoxide at 1000 psi in the presence of cobalt carbonyl brings about insertion of carbon monoxide to form the 1,3-oxazepines S3 <96TL2713>. A convenient route to P-lactams fused to oxepines is made available by alkene metathesis. Thus reaction of 4-acetoxyazetidin-2-one with ally alcohol in the presence of zinc acetate, followed by iV-allylation of the nitrogen affords the derivative 54 which cyclises by RCM to form the oxazepinone 55 <96CC2231>. The same communication describes a similar synthesis of 1,3-dioxepines. 

Epoxidation of ally alcohol and allyl chloride—influence of pH... 

Epoxidation of ally alcohol with H202 in various solvents... 

Reaction of the allyltitaniums with D20 and NCS proceeds with excellent regioselectiv-ity, and thus a new one-pot method for converting ally] alcohol derivatives to 1-alkenes having D and Cl at the allylic position is opened up (Eq. 9.26) [46]. 

The ruthenium-catalyzed direct addition of saturated aliphatic alcohols to non-activated alkynes remains a challenge. Only ally alcohol has been successfully involved in the intermolecular addition to phenylacetylene to produce an ether and the enal resulting from Claisen rearrangement (Equation 10.7) [24]. Thus, in refluxing toluene, in the presence of a catalytic amount of RuCl(tris(pyrazolyl) borate) (pyridine)2, a 1 1 mixture of ally P-styryl ether and 2-phenylpent-4-enal was obtained in 72% overall yield. 

From a-substituted allylic alcohols, the formation of p,y-unsaturated ketones is favored, whereas conjugated enones are obtained from simple ally alcohol [46]. This transformation of terminal alkynes via coupling with allylic alcohol and formation of a C—C bond with atom economy has been applied to the synthesis and modification of natural compounds such as rosefuran and steroids [48, 49]. 

Blechert et al. succeeded in intermolecular CM of terminal alkyne and terminal alkene. A reaction carried out in CH2CI2 at RT in the presence of 5-7mol% Ic gives a mixture of ( )- and (Z)-isomers (Table 2). Because of the nonselective stereochemical course, a silyl-protected ally alcohol is employed and the resulting metathesis product is deprotected and oxidized to afford the desired diene having an -configuration (Equation (13)). 

The world s manufacturers of ally] alcohol are ARCO Chemical Company, Show a Denko K.K., Daicel Chemical Industries, and Rhone-Poulenc Chimie lolal production is approximately 70.000 tons per year. 

Mixtures of regioisomers are frequendy obtained in these reactions.80 The problem is most serious with primary allylic alcohols without a- or p-substituents. Even the 2-arylated products generally rearrange to saturated aldehydes. Ally alcohol itself, when reacted with iodobenzene and triethylamine, with palladium acetate as catalyst, for example, produces a 71 % yield of an 84 16 mixture of 3-phenyl- and 2-phenyl-propanal (equation 28). 

Let s take these three chiral synthons in turn. First, the simplest one the central epoxide. The reagent we need here will carry a leaving group, such as a tosylate, and it can easily be made from the epoxy-alcohol. This gives a very good way of making this compound as a single enantiomer—a Sharpless asymmetric epoxidation of ally] alcohol. 

We may consider some chemical examples. Several alcohols, including ethanol and ally alcohol, have been studied using the density domain shape analysis approach [2,3], and in all these cases a whole range [a, a"] of density threshold values have been found within which the O and H nuclei of the OH group are completely surrounded by MIDCO s, separating these nuclei from all the other nuclei of the molecule. This criterion, the existence of a MIDCO that separates a group of nuclei from all other nuclei of a molecule, is used for the identification and a detailed characterization of chemical functional groups [1-3]. 

Bomeol, ferf-butyl alcohol d-camphor, cineol, pentamethyl ethyl alcohol Ally) alcohol, cyanogen, formaldehyde, formic acid, methylisothiocyanate Acetylene, carbon tetrachloride, chloroform, ethylene dichloride, propyl alcohol... 

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