Stereospecific Conjugate Alkenyl Group Transfer to α,β-Enones Using Vinylalane Reagents

Hooz, John; Layton, Robert B.

doi:10.1139/v73-314

Cited by 28 publications

(7 citation statements)

References 13 publications

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“…2Et2AlCH=CHEt -(Et2Al)2CHCH(Et)CH=CHEt (5) R2A1CH=CHR compounds can be stabilized for long-term storage by complex formation with at least an equimolar amount of an ether such as THF or diethyl ether. Figure 1 gives the results of experiments in which THF and diethyl ether complexes with freshly prepared Et2AlCH=CHEt were allowed to age along with control samples.…”

Section: Hx_/h /C C\mentioning

confidence: 99%

“…The main product was shown to be identical with an authentic sample ofeis-3-hexen-l-ol from Norda Essential Oils. Product characterization: IR 2.99, 3.33, 3.38,3.48,4.24,6.03,6.85,9.55,9.77,11.18,11.58 µ; NMR (CCh, Me4Si internal standard) 5.35 (m, 2, -CHa=CHb-, Jab -6 Hz), 3.7 (s, 1, -OH), 3.53 (t, 2, -CH20), 2.2 (m, 4, protons a to double bond), 0.96 (t, 3, CH3-).…”

Section: Synthesis Of Alcoholsmentioning

confidence: 99%

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Unsaturated aluminum alkyls. Stabilization and reaction with epoxides

Malpass¹,

Watson²,

Yeargin³

1977

J. Org. Chem.

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A general procedure for synthesis of bicyclo[n.2.0]alkane-l,n-diols is described. The synthesis involves thermal cycloaddition of dichloroketene to a cyclic alkene to generate the bicyclic skeleton (e.g., 6), cine substitution with a carboxylate anion to give a bridgehead oxygen substituent (e.g., 12), removal of the remaining halogen with chromous chloride, and reduction to give diol (e.g., 14). The procedure allows for the synthesis of either cis or trans diols selectively.

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Section: Hx_/h /C C\mentioning

confidence: 99%

Section: Synthesis Of Alcoholsmentioning

confidence: 99%

Unsaturated aluminum alkyls. Stabilization and reaction with epoxides

Malpass¹,

Watson²,

Yeargin³

1977

J. Org. Chem.

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“…In analogy to their studies on alkynylalanes, Hooz and Layton examined reactions of diisobutyl[(E)-hex-1enyl]aluminum with various enones and determined that the regioselectivity is governed by essentially the same factors. 26 Thus, conjugate addition only occurred in the case of enones capable of adopting a cisoidal conformation and when using hydrocarbons or mixtures of hydrocarbons and diethyl ether as solvent. With tetrahydrofuran as the solvent, or in the case of transoidal enones, no 1,4addition took place, but complex mixtures were obtained, presumably stemming from 1,2-addition and subsequent decomposition of the thus-formed highly sensitive diallyl-ic alcohols.…”

Section: Scheme 2 Predominant 12-addition Of Aletmentioning

confidence: 99%

Selectivity Control in 1,2- and 1,4-Additions of Aluminum Organyls to Carbonyl Compounds

Zezschwitz¹

2008

Synthesis

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Aluminum organyls are valuable reagents for carboncarbon bond formation as they can either be purchased at low prices or conveniently be prepared, for example, by hydro-or carboalumination of alkenes and alkynes. Although their application in reactions with a,b-unsaturated carbonyl compounds is rather limited, it creates a diverse picture concerning the selectivity of product formation which depends on several factors such as the type of organic residue, the conformation of the enone, the presence of additional functional groups and the donor ability of the solvent. This review describes issues of selectivity of such uncatalyzed transformations as well as conjugate additions catalyzed by achiral copper and nickel catalysts in which alanes can act similarly or even superiorly to the more common lithium or magnesium organyls. Moreover, the rapidly growing field of transition-metal-catalyzed asymmetric 1,2and 1,4-additions is reviewed, in which aluminum reagents can not only lead to enantioselective alkyl additions, thus substituting zinc organyls, but also afford introduction of aryl, alkenyl and alkynyl groups. 1 Introduction 2 Uncatalyzed Additions to a,b-Unsaturated Carbonyl Compounds 2.1 Regioselectivity with Plain Enones 2.2 Selective Conjugate Additions to Cyclic Enones 2.3 Conjugate Additions to Carboxylic Compounds 3 Racemic Copper-and Nickel-Catalyzed 1,4-Additions 4 Asymmetric Addition to Carbonyl Compounds 4.1 Enantioselective Conjugate Additions to Enones 4.2 Enantioselective 1,2-Additions 5 Conclusion

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“…Alkenylation reactions have also been investigated. Organometallic alkenylation of activated olefins has been widely described and generally involves organocopper, 17,44 organoborane, 45,46 organoalane, 47 organozirconium, 48 and organomanganese. 49 The reaction conditions used for performing the nickel-catalyzed electrochemical conjugate addition of 1-alkenyl halides 50 are similar to those used for the arylation reaction.…”

Section: Scheme 14mentioning

confidence: 99%