Asymmetric intramolecular Diels-Alder reactions of sulfoximine-activated trienes

Craig, Donald C.; Geach, N. J.; Pearson, Christopher J.; Slawin, Alexandra M. Z.; White, Andrew J. P.; Williams, David J.

doi:10.1016/0040-4020(95)00267-c

Cited by 28 publications

(13 citation statements)

References 27 publications

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“…Neverthelessat least from a stereochemical point of viewthey perform very poorly in 1,3-dipolar cycloadditions 252 and Diels-Alder reactions. [253][254][255] In 1984 a number of vinyl sulfoximines were prepared in racemic and optically active states and their reaction with cyclohexa-1,3-diene was studied (Scheme 109). 254…”

Section: Type Iia: Pericyclic Reactionsmentioning

confidence: 99%

“…Interestingly, things did not improve very much with intramolecular Diels-Alder reactions which were intensively studied by Craig et al (Table 6). 122,123,253,255 A series of N-substituted sulfonimidoyl-1,6,8-nonatrienes 434 (n = 1) and 1,7,9-decatrienes 434 (n = 2) were synthesised via Wittig-Horner chemistry or the AEI-route em- The intramolecular Diels-Alder reaction of the methyl substituted derivative 435 (n = 1, X = Tf) was only modestly trans selective (9:1) but completely selective for one diastereomer in the trans-and in the cis-fused-series, respectively. The reactions of 435 (n = 2, X = Ts) and 435 (n = 2, X = Tf) exhibit low selectivities (6:1 and 4:1, respectively) with the cis isomers 442 predominating.…”

Section: Scheme 109mentioning

confidence: 99%

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Sulfoximines: Structures, Properties and Synthetic Applications

2000

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This review presents a comprehensive treatment of sulfoximine chemistry particularly emphasising synthetic developments and structural work after 1985. Following a brief introduction, the structures and properties of sulfoximines and metallated sulfoximines are discussed. The second section deals with the preparation of sulfoximines emphasising new methods. The main part of the review is concerned with reactions of sulfoximines. The material in this section is organised based on the reactivity pattern displayed by the various sulfoximines. Therefore they are grouped roughly into three classes of compounds. The first group of sulfoximines comprises compounds acting as C-nucleophiles, the second one contains electrophilic sulfoximines and the last group is made up of sulfoximines being useful as (chiral) ligands particularly for transition metals. Finally the ability of sulfoximines to act as "chiral chemical chameleons" and their rôle in biological and medicinal chemistry is briefly discussed.

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Section: Type Iia: Pericyclic Reactionsmentioning

confidence: 99%

Section: Scheme 109mentioning

confidence: 99%

Sulfoximines: Structures, Properties and Synthetic Applications

2000

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“…Phenols can be ether linked to the diene component, oxidised to the corresponding parabenzoquinone mono-ketals which then undergo in situ IMDA reactions, to give cis-decalins fused to furan rings reminiscent of certain diterpenes (equation 7) 63 . Sulphones (Scheme 14; equation 1) 64 , sulphoximines (equation 2) 65 and vinyl sulphonates (equation 3) 66 have been shown to be excellent dienophile electron withdrawing groups, and their cycloadducts are clearly of synthetic relevance. An interesting sequence of pericyclic reactions includes a [3,3] sigmatropic rearrangement, COS extrusion to a sulfide chain and finally an IMDA reaction (Scheme 14; equation 4) leading preferably to cis-fused cycloadducts, and this selectivity is supported by ab initio calculations 67 .…”

Section: Tethers In Imda Reactionsmentioning

confidence: 99%

The Diels-Alder reaction: an update

Brocksom

Nakamura

Ferreira

et al. 2001

J. Braz. Chem. Soc.

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“…The influence of the phenylsulfonylallenyl terminus on the reactivity of 5c is also highlighted by comparing the IMDA reaction of (6E)-1-phenylsulfonylnona-1,6,8triene, which requires heating at 140 °C for 44 h for complete reaction (80 % yield of a 1:1 mixture of diastereomers). 12 Clearly, the introduction of the additional olefinic bond has a significant effect on both reactivity and selectivity.…”

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confidence: 99%

The 1-Phenylsulfonylallenyl Terminus in Intramolecular Diels-Alder Reactions: Tether Length and Reactivity

Bull¹,

Gordon²,

Hunter³

1999

Synlett

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Methods are described for the synthesis of 1-phenylsulfonylalka-1,2,(n + 4),(n + 6)-tetraenes 5 (n = 2 -4), and preliminary findings on their thermally-induced intramolecular cycloaddition behaviour are reported. The reaction of 5 (n = 4) is slow, and engages the unactivated π-bond, whereas those of 5 (n = 2 & 3) proceed readily and exo-selectively with dienophilic participation of the activated terminal π-bond, to give the expected [4 + 2] cycloadducts. The reactivity of 5 (n = 2) is particularly noteworthy since cycloaddition proceeds under exceptionally mild conditions. The well-known advantages of intramolecular Diels-Alder (IMDA) reactions for assembling complex ring systems 1 continue to promote the development and application of new methodology. Recently, there have been several reports 2 on the use of the allenyl functionality as the dienophilic partner in IMDA methodology, but hitherto, with little evidence of emergence of a general pattern of structure-reactivity and selectivity.As part of our programme of investigation into the dienophilic utility of variously functionalised allenes, 3 we report the preliminary findings resulting from synthesis and IMDA reactions of 1-phenylsulfonylallenyl compounds, terminally substituted with appropriate butadienyl functionality. In the first phase of this investigation, we set out to establish the levels of intramolecular cycloaddition reactivity and periselectivity associated with variations in the tether length between the participating 1-phenylsulfonylallenyl and butadienyl termini. The C 9 -C 11 model systems were thus chosen, in the reasonable expectation that they would accommodate favourable transition state geometries for this purpose, and would be expected to yield functionalised bicyclic cycloadducts of synthetic utility.The starting (E)-alka-(n + 2),(n + 4)-dien-1-ols 1 (n = 2 -4) were prepared in accordance with standard literature methods. 4 -7 Swern or Dess-Martin 8 oxidation of 1 furnished the corresponding aldehydes 2, which were ethynylated to give the dienynols 3 in good to moderate yields (Scheme 1). Treatment of these intermediates at -78 °C with benzenesulfenyl chloride readily resulted in formation of the 1-phenylsulfinylallenyl dienes 4, via [2,3] sigmatropic rearrangement of the primary phenylsulfenyl esters. 9 Oxidation of the sulfoxides 4 with m-CPBA proceeded smoothly and, generally, chemoselectively at 0 °C to give the corresponding 1-phenylsulfonylalka-1,2,(n + 4),(n + 6)-tetraenes 5. With one exception (5c; see below), these were stable products which were fully characterised. 10 The E/Z ratios of 5a,b and d were in excess of 95 % and reflect those of the precursors 1. Scheme 1. (a R = H, n = 4; b R = H, n = 3; c R = H, n = 2; d R = Me, n = 2) Reagents. (i) (COCl) 2 , DMSO, CH 2 Cl 2 , NEt 3 , -60 °C; (ii) HCCMgBr, THF, 20 °C; (iii) PhSCl, NEt 3 , CH 2 Cl 2 , -78 °C; (iv) m-CPBA, CH 2 Cl 2 , -0 °C Intramolecular cycloadditions of 5a and 5b were conducted in toluene (sealed tube) at temperatures which were determined by reasonable rates ...

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Asymmetric intramolecular Diels-Alder reactions of sulfoximine-activated trienes

Cited by 28 publications

References 27 publications

Sulfoximines: Structures, Properties and Synthetic Applications

Sulfoximines: Structures, Properties and Synthetic Applications

The Diels-Alder reaction: an update

The 1-Phenylsulfonylallenyl Terminus in Intramolecular Diels-Alder Reactions: Tether Length and Reactivity

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