Hydrohalogenation Reaction of 1,2-Allenic Sulfoxides with AlX3 and H2O: Efficient Synthesis of 2-Haloallyl Sulfoxides

Ma, Shengming; Qi, Wei

doi:10.1002/(sici)1099-0690(200005)2000:10<1939::aid-ejoc1939>3.0.co;2-v

Cited by 34 publications

(5 citation statements)

References 29 publications

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“…Cl OH n-C 6 The corresponding reaction of 2,3-octadienoic acid or 2,3-nonadienoic acid with LiBráH 2 O or LiCl·H 2 O afforded a lower ratio of two stereoisomers (Z)-2 and (E)-2 (entries 1, 2, 4, and 5, Table 1). The two stereoisomers of the corresponding bromides can also be separated by column chromatography on silica gel.…”

Section: Figurementioning

confidence: 55%

Hydrohalogenation Reaction of Substituted 1,2-Allenic Carboxylic Acids, Esters, Amides, Nitriles, and Diphenyl Phosphine Oxides

Ma¹,

Xie²,

Wang³

et al. 2001

Synthesis

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The hydrohalogenation reaction of 1,2-allenic carboxylic acids, esters, amides, nitriles, and diphenyl phosphine oxides with HX or MX (X = I, Br, Cl, M = Na, Li) in different solvents, such as HOAc, CF 3 CO 2 H, and CF 3 CO 2 H-HOAc (1:1) was studied. The reaction is a nucleophilic conjugate addition in nature and provides efficient entries to 3-halo-3-enoic acids, esters, amides, nitriles, and 2-haloallyl diphenyl phosphine oxides. The b,g-over a,b-selectivity and stereoselectivity depend on the solvent(s) and the temperature applied. In most cases, the Z-and E-isomers can be easily separated by chromatography on silica gel. The subsequent cross-coupling reaction with organometallic reagents and terminal alkynes showed the synthetic potential of these products.3-Alkenoic acids as well as their derivatives and 2-haloallyl phosphine oxides are classes of compounds with synthetic importance due to the uniquely located carboncarbon double bonds. Recently during the course of our study on the chemistry of allene, 1,2 we developed the hydrohalogenation reaction of electron-deficient allenes, 3 such as 1,2-allenyl ketones, 4,5 carboxylic acids, 4 esters, 4 sulfoxides, 6 and sulfones 7 to afford b-halo-b,g-unsaturated functionalized alkenes. A challenge encountered here is the potential migration of the C=C bond from the bhalo-b,g-position to the a,b-position, thus, affording a synthetically useless mixture of b,g-unsaturated products and a,b-unsaturated products. 4,5,8 In a preliminary communication 9 we have demonstrated that the hydrohalogenation reaction of 2-alkyl-2,3-dienoates with MX in CF 3 COOH-HOAc or CF 3 COOH afforded 2-alkyl-3-halo-3-alkenoates with a high selectivity. Here, the reaction medium is the key to avoid the formation of a mixture of b,g-unsaturated and a,b-unsaturated products. In this paper we wish to report our recent results of the hydrohalogenation reaction of differently substituted 2,3-dienoic acids, esters, amides, nitriles, and 1,2-allenyl phosphine oxides and the corresponding synthetic application of the b,g-unsaturated 3-halo-3-alkenoates, b,g-unsaturated 3-halo-2-alkenenitriles, and b,g-unsaturated 2-halo-2-propenyl diphenyl oxides.Hydrohalogenation Reaction of Substituted 1,2-Dienyl Carboxylic Acids. The results of the reaction of 2,3-octadienoic acid with NaI under different conditions are summarized in Scheme 1. Scheme 1Scheme 1 shows that the reaction already occurs at room temperature but the stereoselectivity is higher at a higher reaction temperature. After 6.5 h under reflux the reaction afforded product 2 in 95 % yield with a Z/E ratio of 9.4:1; the products (E)-2aa and (Z)-2aa can be separated by column chromatography on silica gel, providing synthetically useful entries to both Z-and E-isomers of 3-iodo-2-alkenoic acids and derivatives.COOH n-C 4 H 9

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Section: Figurementioning

confidence: 55%

Hydrohalogenation Reaction of Substituted 1,2-Allenic Carboxylic Acids, Esters, Amides, Nitriles, and Diphenyl Phosphine Oxides

Ma¹,

Xie²,

Wang³

et al. 2001

Synthesis

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“…of water are the most efficient. 17 Under the reaction conditions, hydrohalogenation reactions of 1,2-allenic sulfoxides with AlBr 3 or AlCl 3 afforded the corresponding 2-haloallylic sulfoxides with yields ranging from 56% to 89%. The reaction with AlBr 3 was less efficient than the hydrochlorination reaction with AlCl 3 .…”

Section: Methodsmentioning

confidence: 99%

An Efficient New Methodology for the Synthesis of 1-Functionalized 2-Halo-2-alkenes via Hydrohalogenation Reaction of Electron-Deficient Allenes

Ma¹,

Li²

2001

Synlett

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The hydrohalogenation reactions of electron-deficient allenes, such as 1,2-allenic ketones, carboxylic acids, esters, amides, nitriles, sulfoxides (with the use of AlX 3 /H 2 O), sulfones, and phosphine oxides with MX (X = I, Br, Cl, M = Na, Li) in different solvents, such as HOAc, CF 3 COOH-HOAc (1:1), CF 3 COOH and THF were studied. The reaction is nucleophilic conjugate addition in nature and provides efficient entries to 1-functionalized 2-halo-2-alkenes. The b,gover a,b-selectivity and stereoselectivity depend on the solvent(s) and the temperature applied. In most cases, the Z-and E-isomers can be easily separated with chromatography on silica gel. The subsequent cross coupling reaction with organometallic reagents and terminal alkynes showed the synthetic potential of these products. 10 Synthetic Application 11 Conclusion

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“…Some examples are found in the reaction of alkenes with p -toluenesulfinamide catalyzed by Yb(III) and trimethylsilyl chloride (TMSCl) or with PhSOCl and ZnCl 2 or EtAlCl 2 . Allenyl sulfoxides react with AlCl 3 to provide 2-haloallyl sulfoxides, α-lithio sulfinyl carbanions give allylic sulfoxides by reaction with Cr and W Fischer carbenes, and β-sulfinylesters 76 generate sulfenate anions in basic media that are trapped with allylic acetates under Pd(0) catalysis to generate allylic sulfoxides 77 – 79 with different substitution (Scheme ). , …”

Section: Synthesis Of Allylic Sulfoxidesmentioning

confidence: 99%

From Allylic Sulfoxides to Allylic Sulfenates: Fifty Years of a Never-Ending [2,3]-Sigmatropic Rearrangement

et al. 2017

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The [2,3]-sigmatropic rearrangement of allylic sulfoxides to allylic sulfenates is a reversible process, generally shifted toward the sulfoxide. In the presence of thiophiles, the sulfenate is trapped, and allylic alcohols are obtained under mild conditions. In most cases, a good transfer of stereochemical information through an ordered transition state is obtained. Furthermore, the ease of coupling this process with other versatile, stereocontrolled reactions has enhanced the usefulness of this protocol. This review aims to provide a comprehensive survey of this rearrangement and its application in the synthesis of natural and bioactive products.

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Hydrohalogenation Reaction of 1,2-Allenic Sulfoxides with AlX3 and H2O: Efficient Synthesis of 2-Haloallyl Sulfoxides

Cited by 34 publications

References 29 publications

Hydrohalogenation Reaction of Substituted 1,2-Allenic Carboxylic Acids, Esters, Amides, Nitriles, and Diphenyl Phosphine Oxides

Hydrohalogenation Reaction of Substituted 1,2-Allenic Carboxylic Acids, Esters, Amides, Nitriles, and Diphenyl Phosphine Oxides

An Efficient New Methodology for the Synthesis of 1-Functionalized 2-Halo-2-alkenes via Hydrohalogenation Reaction of Electron-Deficient Allenes

From Allylic Sulfoxides to Allylic Sulfenates: Fifty Years of a Never-Ending [2,3]-Sigmatropic Rearrangement

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