A dual metathesis route to oligomeric sulfonamides

Wanner, Jutta; Harned, Andrew M.; Probst, Donald A.; Poon, Kevin W. C.; Klein, Thomas A.; Snelgrove, Kelley A; Hanson, Paul R.

doi:10.1016/s0040-4039(01)02293-6

Cited by 47 publications

(24 citation statements)

References 42 publications

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“…Biologically active polymers 16 containing sulfonamide groups have been synthesized by ROMP with the Grubbs catalysts 11 and 12. 47 A tripeptide motif, the arginine-glycine-aspartic acid (RGD) sequence, occurs in cellular matrix proteins. 48 Recent advances in ROMP S Sutthasupa et al analogous polymers 50 have been synthesized by ROMP.…”

Section: Synthesis Of Amino Acid-and Peptide-based Polymers By Rompmentioning

confidence: 99%

Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials

Sutthasupa

Shiotsuki

Sanda

2010

Polym J

339

273

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This article reviews the development of catalysts for ring-opening metathesis polymerization (ROMP), synthesis of polymers bearing amino acids and peptides by ROMP of functionalized norbornenes, formation of aggregates and micelles, and applications of the polymers to medical materials. It also describes the control of monomer unit sequences, that is, living polymerization to synthesize block copolymers, and alternating copolymerization that is achieved on the basis of acid-base interactions. Polymer Journal (2010) 42, 905-915; doi:10.1038/pj.2010.94; published online 13 October 2010Keywords: alternating copolymerization; amino acid; block copolymerization; living polymerization; metathesis catalyst; peptide; ROMP INTRODUCTIONOlefin metathesis reactions are metal-mediated carbon-carbon (C-C) double bond exchange processes, 1,2 which were discovered in the mid 1950s. Chauvin proposed the commonly accepted mechanism for metathesis involving a metallacyclobutane, as illustrated in Scheme 1. 3 Initially, olefin metathesis was regarded as an odd reaction, but now it has undoubtedly established the position as one of the most important C-C bond formation reactions applicable to synthesis of a wide variety of useful products. In the early stages, transition metal chlorides were used as catalysts for the reaction, but the transition metal carbene complex catalysts designed by Schrock and Grubbs have remarkably advanced mechanistic analysis and control of catalytic activity by the choice of ligands. In 2005, Chauvin, Grubbs and Schrock were awarded the Nobel Prize in chemistry for development of the metathesis method in organic synthesis.Olefin metathesis polymerization is an application of metathesis reactions to polymer synthesis and includes ring-opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) polycondensation (Scheme 2). ADMET has been extensively developed by Wagener since 1987 4 for the synthesis of polyolefins having regularly spaced functional group branches and high thermal stability and crystallinity. 5,6 ADMET is also useful for synthesizing polymeric materials containing in-chain functionality. Although the general structures of the polymers obtained by ROMP and ADMET are illustratable in the same fashion as shown in Scheme 2, a completely different treatment is necessary from the viewpoint of polymerization kinetics. The former involves chain polymerization, whereas the latter is a step-growth polymerization process.

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Section: Synthesis Of Amino Acid-and Peptide-based Polymers By Rompmentioning

confidence: 99%

Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials

Sutthasupa

Shiotsuki

Sanda

2010

Polym J

339

273

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“…For five-and six-membered-ring benzosultams, see [43]. For potential intramolecular H-bonding of a five-membered-ring, free sultam, see [44]. For structure determination and intermolecular H-bond analyses of a sulfonamide, based on powder diffraction data associated with solid-state NMR, see [45].…”

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confidence: 99%

Comparative Infrared, Raman, and Natural‐Bond‐Orbital Analyses of King's Sultam

Hagemann

Dułak

Wesołowski

et al. 2004

Helvetica Chimica Acta

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Dedicated to Dr. G¸nther Ohloff on the occasion of his 80th anniversary By means of 1 H-NOESY-and Raman-spectroscopic analyses, we experimentally demonstrated the presence of the equatorial NÀMe conformer of King×s sultam 4b in solution, resulting from a rapid equilibrium. As a consequence, the value of the N lone-pair anomeric stabilization should be revised to 1.5 ± 1.6 kcal/mol. Independently from the N tilting, natural bond orbital (NBO)-comparative analyses suggest that the S d* orbitals do not appear as primordial and stereospecific acceptors for the N lone pair. Second, the fivemembered-ring sultams do not seem to be particularly well-stabilized by the SÀC s* orbital in the N-substituted pseudo-axial conformation, as opposed to an idealized anti-periplanar situation for the six-membered-ring analogues. In this latter case, the other anti-periplanar CÀC s* and C(1')ÀH/C(2') s*orbitals are as important, if not more, when compared to the SÀC s* participation. In the pseudo-equatorial conformation, g-sultams particularly benefit from the N lone-pair hyperconjugation with the anti-periplanar SÀO 1 s* and C(2)ÀH/C or C(1')ÀH/C s* orbitals. This is also the case for d-sultams when the steric requirement of the N-substituent exceeds 1.6 kcal/mol. When both axial and equatorial conformations are sterically too exacting, the N-atom is prone to sp 2 hybridization or/and conformational changes (i.e., 12c). In that case also, the mode of stereoelectronic stabilization differs from g-to d-sultams.Introduction. ± Based on semi-empirical calculations, we proposed in [1] that the steric origin of the diastereoselectivity imparted to N-a,b-enoyl derivatives by g-sultam auxiliaries of type 1 2 ) and 2 [6], as rationalized by Kim and Curran [7], is modulated by the stereoelectronic influence of the N lone pair (lp). We stressed that this additional effect, which is, under unchelating conditions, either matching or mismatching the steric approach, depending on the syn-or anti-s-cis conformations of the N-a,b-enoyl side chain, results from a general anomeric influence [8] 3 ) of the N lp, through the sp 2 CO, on the LUMO p-facial electronic distribution of the reactive centers. The N lp is itself orientated by stabilization with the anti-periplanar SÀO 1 s* orbital. We later

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“…4,127.4,128.3 (CPh) (17), 106 (7), 105 (47), 84 (24), 83 (37), 77 (8), 70 (9), 67 (9), 55 (11), 54 (7), 46 (7), 45 (16). MS (CI): m/z (%) = 411 (21), 410 (15), 409 (10), 363 (19), 357 (17), 330 (14), 329 (78), 327 (14), 311 (7), 281 (9), 245 (7), 243 (10), 217 (6), 216 (11), 214 (100), 203 (6), 197 (14), 132 (15), 129 (18), 105 (12). C 21 H 34 N 2 O 4 S (410.57) calcd.…”

Section: Cyclohexyl (S)-(-)-4-[2-(methoxymethyl)pyrrolin-1-ylimino]buunclassified

“…[1a,16] In 1999, Hanson et al described the first synthesis of cyclic sulfonamides with metathesis reactions, [17] and a few years later they reported on the successful enantioselective synthesis of γ-sultams. [18] Moreover, Metz et al described the synthesis of bicyclic δ-sultams by intramolecular Diels-Alder reactions of vinylsulfonamides. [19] As part of our continuous interest in the asymmetric synthesis of sulfur-containing heterocycles, [20] we already described the diastereo-and enantioselective synthesis of cis-3,4-disubstituted β-sultams.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Synthesis of 3‐Substituted γ‐ and δ‐Sultams

2006

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An efficient and flexible asymmetric synthesis of various 3-substituted γ-and δ-sultams is described. The key step is a diastereoselective nucleophilic 1,2-addition of various organocerium compounds to the CN double bond of ω-SAMP-hydrazonosulfonates. The resulting hydrazines were obtained in good to excellent diastereomeric excesses (de = 78 to Ն 96 %). Removal of the chiral auxiliary by reductive N,N-bond cleavage afforded the corresponding aminosulfonates without racemisation. Ester hydrolysis and subsequent treatment

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A dual metathesis route to oligomeric sulfonamides

Cited by 47 publications

References 42 publications

Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials

Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials

Comparative Infrared, Raman, and Natural‐Bond‐Orbital Analyses of King's Sultam

Asymmetric Synthesis of 3‐Substituted γ‐ and δ‐Sultams

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