Sulfur Dioxide Promotes Its Hetero-Diels−Alder and Cheletropic Additions to 1,2-Dimethylidenecyclohexane

Fernández, T.; Sordo, José; Monnat, Frédéric; Deguin, Brigitte; Vogel, Pierre

doi:10.1021/ja982565p

Cited by 33 publications

(40 citation statements)

References 14 publications

(14 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The observation that sultine 6f is formed preferentially (sultine 5f/6f ratio of 1 : 4) suggests, therefore, that the regioselectivity of that hetero-Diels-Alder addition is governed by the stability difference between the two sultines 5f and 6f, rather than by kinetic control. The model of the diradicaloids of the transition structures of the hetero-Diels-Alder additions of SO 2 predicts also that these reactions are catalyzed by Broenstedt and Lewis acids, as observed, and as predicted also by high-level quantum calculations of these reaction hypersurfaces [12] [15]. It can be applied to predict the regioselectivity of the hetero-Diels-Alder additions of SO 2 to 1-substituted buta-1,3-dienes.…”

mentioning

confidence: 81%

See 1 more Smart Citation

Competition between Hetero-Diels-Alder and Cheletropic Additions of Sulfur Dioxide to 2-Substituted Buta-1,3-dienes. Synthesis of 2-(1-Naphthyl)- and 2-(2-Naphthyl)buta-1,3-diene

Roversi¹,

Vogel²

2002

HCA

Self Cite

View full text Add to dashboard Cite

Chloroprene ( 2-chlorobuta-1,3-diene; 4b) and electron-rich dienes such as 2-methoxy-(4c), 2-acetoxy-(4d), and 2-(phenylseleno)buta-1,3-diene (4e) refused to equilibrate with the corresponding sultines 5 or 6 between À 80 and À 108 in the presence of excess SO 2 and an acidic promoter. Isoprene (4a) and 2-(triethylsilyl)-(4f), 2-phenyl-(4g), and 2-(2-naphthyl)buta-1,3-diene (4i) underwent the hetero-Diels-Alder additions with SO 2 at low temperature. In contrast, 2-(1-naphthyl)buta-1,2-diene (4h) did not. With dienes 4a, 4g, and 4i, the heteroDiels-Alder additions with SO 2 gave the corresponding 4-substituted sultine 5 with high regioselectivity. In the case of 4g SO 2 >5g, the energy barrier for isomerization of 5g to 5-phenylsultine (6g) was similar to that of the cheletropic addition of 4g to give 3-phenylsulfolene (7g). The hetero-Diels-Alder addition of 4f gave a 1 : 4 mixture of the 4-(triethylsilyl)sultine (5f) and 5-(triethylsilyl)sultine (6f). The preparation of the two new dienes 4h and 4i is reported. Introduction. ± In the two preceding reports [1] [2], we have demonstrated that the competition between hetero-Diels-Alder and cheletropic additions of sulfur dioxide depends strongly on the nature of the conjugated dienes. At low temperature (À 808) and in the presence of an acidic promoter, SO 2 adds to (E)-1-alkylbuta-1,3-diene (E)-1a giving, in agreement with the endo Alder rule [2], the corresponding cis-6-alkyl-2,6-dihydro-1,2-oxathiin 2-oxides (cis-sultines c-2a), which then equilibrate with their more stable trans-isomers (trans-sultines t-2a) (Scheme 1).

show abstract

mentioning

confidence: 81%

“…The structures of the major sultine 6f was confirmed by its 2D 1 H, 1 H-NOESY data (significant cross-peaks for H a ÀC(3) (3.66 ppm)/HÀC(4) (6.23 ppm), H e ÀC(3) (3.23 ppm)/HÀC(4), H a ÀC(6) (4.72 ppm)/Et 3 Si, and H e ÀC(6)/ Et 3 Si). The pseudo-axial position of the SO moieties is proposed, as predicted by high-level quantum calculations [12] [15].…”

mentioning

confidence: 99%

Competition between Hetero-Diels-Alder and Cheletropic Additions of Sulfur Dioxide to 2-Substituted Buta-1,3-dienes. Synthesis of 2-(1-Naphthyl)- and 2-(2-Naphthyl)buta-1,3-diene

Roversi¹,

Vogel²

2002

HCA

Self Cite

View full text Add to dashboard Cite

show abstract

“…The model of the diradicaloids of the transition structures of the hetero-Diels-Alder additions of SO 2 predicts also that these reactions are catalyzed by Br˘nsted and Lewis acids, as observed, and as predicted also by high-level quantum calculations of these reaction hypersurfaces [13] [14]. It can be applied to predict the regioselectivity of the hetero-Diels-Alder additions of SO 2 to 1-substituted buta-1,3-dienes.…”

mentioning

confidence: 85%

“…of 11 had to be prepared by adding cold solvent to frozen 11 in the trap. N,N-Dimethyl(1,2,3,4-tetrahydro-1-methylidenenaphthalen-2-yl)methanamine (13). In a flame-dried 100-ml three-necked flask, Ph 3 P MeBr À (17.8 g, 50 mmol) was suspended in THF (30 ml) under N 2 .…”

Section: Experimental Partmentioning

confidence: 99%

Synthesis of 1,2,3,4-Tetrahydro-1,2-dimethylidenenaphthalene: A Reactive s-cis-Butadiene Undergoing Highly Chemo- and Regioselective Cyclodimerization

Roversi

Vogel

Schenk

2002

HCA

Self Cite

View full text Add to dashboard Cite

“…More recent studies revealed that at the same temperatures the reaction of dimethylidenecycloalkanes with variable ratios of CD 2 Cl 2 /SO 2 produce sultine products without employing acid catalysis. It was also reported that the sultine products isomerized into the corresponding sulfolenes at temperatures above −40 °C [17,18]. Cheletropic reactions of SO 2 and a diene are often carried in the presence of radical inhibitors in order to avoid undesired polymerization of the dienes [19].…”

Section: Recycling Of Sulfolenesmentioning

confidence: 99%

Butadiene sulfone as ‘volatile’, recyclable dipolar, aprotic solvent for conducting substitution and cycloaddition reactions

Huang

Ureña-Benavides

Boigny

et al. 2015

Sustain Chem Process

View full text Add to dashboard Cite

Butadiene sulfone has been employed as a "volatile", recyclable dipolar, aprotic solvent in the reaction of benzyl halide with metal azides to form benzyl azide (1) and the subsequent reaction of benzyl azide with p-toluenesulfonyl cyanide (3) to produce 1-benzyl-5-(p-toluenesulfonyl)tetrazole (2). Comparisons are made with the solvent DMSO and an analogous sulfolene solvent-piperylene sulfone. In addition, recycling protocols for butadiene sulfone and piperylene sulfone are also presented.

show abstract

Sulfur Dioxide Promotes Its Hetero-Diels−Alder and Cheletropic Additions to 1,2-Dimethylidenecyclohexane

Cited by 33 publications

References 14 publications

Competition between Hetero-Diels-Alder and Cheletropic Additions of Sulfur Dioxide to 2-Substituted Buta-1,3-dienes. Synthesis of 2-(1-Naphthyl)- and 2-(2-Naphthyl)buta-1,3-diene

Competition between Hetero-Diels-Alder and Cheletropic Additions of Sulfur Dioxide to 2-Substituted Buta-1,3-dienes. Synthesis of 2-(1-Naphthyl)- and 2-(2-Naphthyl)buta-1,3-diene

Synthesis of 1,2,3,4-Tetrahydro-1,2-dimethylidenenaphthalene: A Reactive s-cis-Butadiene Undergoing Highly Chemo- and Regioselective Cyclodimerization

Butadiene sulfone as ‘volatile’, recyclable dipolar, aprotic solvent for conducting substitution and cycloaddition reactions

Contact Info

Product

Resources

About