Stereoselectivity in the Cycloaddition of Cyclopentadiene toN-Fumaroyl-[2R,S(R)]-Bornane-10,2-sulfinamide Monomethyl Ester

Chapuis, Christian; Kawęcki, R.; Urbańczyk‐Lipkowska, Zofia

doi:10.1002/1522-2675(20010321)84:3<579::aid-hlca579>3.0.co;2-y

Cited by 12 publications

(7 citation statements)

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“…Y. Sugihara and J. Nakayama envisioned, that despite steric hindrance syn-and anti-9,9'-dibenzonorbornenylidenes (128) seemed to be a convenient reagent for [2 + 2]-cycloaddition reaction with tosyl sulfinylaniline. Indeed, this allowed construction of a 1,2-thiazetidine scaffold upon prolonged refluxing in 1,2-dichloroethane.…”

Section: The [2 + 2]- [3 + 2]- and [4 + 2]-cycloaddition Reactions (E...mentioning

confidence: 99%

Cyclic Sulfinamides

Dobrydnev,

Popova,

Volovenko

2023

The Chemical Record

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The literature on cyclic sulfinamides (put simply, sultims) published from 1989 to 2022 has been summarized and reviewed. The information is divided into two sections: the analysis of synthetic methods on the preparation of cyclic sulfinamides and the discussion of the chemical properties of cyclic sulfinamides focusing on their reactions and applications. The survey of the reaction conditions, provided in the most detailed way, and a critical view of the reaction mechanisms add an extra dimension to the text. The data presented will be useful to specialists in different areas, especially those who work in the field of synthetic organic and pharmaceutical chemistry.

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Section: The [2 + 2]- [3 + 2]- and [4 + 2]-cycloaddition Reactions (E...mentioning

confidence: 99%

Cyclic Sulfinamides

Dobrydnev,

Popova,

Volovenko

2023

The Chemical Record

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“…v) NH 4 OH, dioxane, 208; 69%. This conformation also avoids a stereoelectronic destabilizing syn-periplanar orientation of both N/S lp [7]. vii) NaBH 4 , MeOH, H 2 O, 208; 90%.…”

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confidence: 95%

“…Its ability to generally induce high diastereoselectivity at the C(a)-atom of N-(a,b-unsaturated acyloyl) derivatives was rationalized by Kim and Curran on the basis of a steric argument, in which the approach is directed by the C(3) substituent in the chelated syn-s-cis conformation or by the pseudo-axial O(1)S substituent for the nonchelated anti-s-cis conformer [3]. In addition, by comparing structurally analogous dienophiles derived from (À)-1a and (À)-2a [7], we also demonstrated that the anti-s-cis vs. anti-s-trans equilibrium, hence the global diastereoselectivity, were strongly influenced by the pseudo-equatorial O(2)S substituent. Based on results from [4 2] cycloadditions [4] [5] or syn-dihydroxylations [6], we later completed this steric model by hypothesizing the concurrent high reactivity of the syn-s-cis conformer under uncatalyzed conditions [4].…”

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confidence: 99%

Synthesis of a Six-Membered-Ring (2R)-10a-Homobornane-10a,2-sultam and Structural Comparison with Oppolzer's, Lang's, and King's Sultams

Piątek¹,

Chapuis²,

Jurczak³

2002

HCA

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The new six-membered-ring (2R)-10a-homobornane-10a,2-sultam (À)-3a was synthesized and its X-ray structural analysis was compared with that of the novel structure of the five-membered-ring (2R)-bornane-10,2sultam analogues (À)-1a,b as well as with that already published for the six-membered-ring trans-decalin-like sultam 4a. Based on DN** density-function calculations and X-ray crystallographic studies of the N-methylated analogues (À)-1e and 4b and by comparing with the conformation of the N-fluoro derivatives (À)-1c and ()-1d, the anomeric stabilization was estimated to be smaller than the 2.0 ± 2.5 kcal/mol earlier suggested. The direction of pyramidalization is rationalized in terms of H-bond and steric and electronic interactions and extended to the known toluenesultam derivatives 10a ± c. 2 ) For N lp through-bond and through-space directing interactions, initially suggested by M¸ller and Eschenmoser, see [10a]. For nonexhaustive more recent examples, see [10b ± g]. Cieplak also proposed a hyperconjugative influence of the N lp on the incipient bond-formation through the intermediacy of a sp 2 atom, see Schemes 85 and 86 as well as reference 105 in [11]. More recently, King et al. also suggested an anomeric stabilization [12a]. We now wish to report the synthesis of the tricyclic six-membered-ring sultam (À)-3a as well as its X-ray-structural analysis for comparison with those of (À)-1a,b,e and the racemic six-membered-ring trans-decalin-like sultams 4a,b [12a].Results. ± The commercially available ()-camphorsulfonyl chloride 5 was treated with CH 2 N 2 in Et 2 O to afford, after thermal treatment, the known unsaturated C 11 ketone ()-6 in 84% yield according to a previously reported procedure [13]. Further protection of the carbonyl moiety (ethylene glycol, TsOH, THF; 79% yield) followed by hydroboration (9-BBN, THF, 208, then NaOH, H 2 O 2 ; 90% yield) furnished the known primary alcohol (À)-7a [14] 3 ). This intermediate was then converted to the corresponding crude unreported mesylate (À)-7b (MsCl, CH 2 Cl 2 , Et 3 N, 08; 95% yield [16]) prior to an S N 2 displacement (AcSK, DMSO, 458; 96% yield [17]) to afford the thioacetate (À)-7c. Oxidation (30% H 2 O 2 solution, 85%, AcOH solution [18]), with concomitant deprotection, delivered the new sulfonic acid ()-8a in 92% isolated yield. A route similar to that earlier published by Oppolzer et al.[1] was then followed for the preparation of (À)-3a.Thus, treatment with SOCl 2 at 1008 [19] furnished the sulfonyl chloride (À)-8b in 63% yield 4 ). Rather than addition of gaseous NH 3 under anhydrous conditions [21], we preferred, for technical reasons, the NH 4 OH procedure initially reported by Sutherland and co-workers [22] and recently re-actualized by Davis et al. [19] and Capet et al. [23]. The new sulfonamide ()-8c, thus obtained in 69% yield, was then cyclized under basic conditions (NaOMe, MeOH [1]) to furnish the sulfonimine (À)-9 in 75% yield 5 ).Helvetica Chimica Acta ± Vol. 85 (2002) 1974 3 ) According to [15], a lower chemical yield was obtaine...

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“… When a dienophile possessing a modified chiral sulfonamide auxiliary lacking the pseudoequatorial S=O was used for a Diels – Alder cycloaddition, TiCl 4 chelation with the pseudoaxial S=O resulted in total inversion of the π ‐facial selectivity . It is noteworthy that RMgX/Cu(I) and Gilman reagents (R 2 CuLi · PBu 3 ) both induce the same π ‐facial selectivities in both C β and concomitant electrophilic C α additions for very similar Michael acceptors .…”

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Grignard 1,4‐Additions to para‐Substituted (2R)‐N‐Cinnamoylbornane‐10,2‐sultam Derivatives: Revised Configuration for the N,OAc‐Keteneacetal Formation in the Presence of Cu(I)

Piątek

Chapuis

2016

Helvetica Chimica Acta

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Using a 19F‐NMR analytical method, we have corrected and improved the linear correlation initially found between the diastereoselectivity observed during the EtMgBr conjugated addition to Michael acceptors of type 1, as a function of their σpara Hammett electronic parameters. Based on 1H‐NMR analyses, we have also discovered that the original configuration of the acetylated intermediate, obtained by either hydride, Grignard, or cuprate conjugate additions to α‐substituted N‐enoyl bornane‐10,2‐sultams was initially erroneously attributed by Oppolzer et al. A new, much simpler rationalization for these 1,4‐additions has now been proposed.

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Stereoselectivity in the Cycloaddition of Cyclopentadiene toN-Fumaroyl-[2R,S(R)]-Bornane-10,2-sulfinamide Monomethyl Ester

Cited by 12 publications

References 11 publications

Cyclic Sulfinamides

Cyclic Sulfinamides

Synthesis of a Six-Membered-Ring (2R)-10a-Homobornane-10a,2-sultam and Structural Comparison with Oppolzer's, Lang's, and King's Sultams

Grignard 1,4‐Additions to para‐Substituted (2R)‐N‐Cinnamoylbornane‐10,2‐sultam Derivatives: Revised Configuration for the N,OAc‐Keteneacetal Formation in the Presence of Cu(I)

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