Phosphine‐Catalyzed Synthesis of Chiral <i>N</i>‐Heterocycles through (Asymmetric) P(III)/P(V) Redox Cycling

Lorton, Charlotte; Saleh, Nidal; Voituriez, Arnaud

doi:10.1002/ejoc.202100404

Cited by 6 publications

(4 citation statements)

References 66 publications

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“…This new strategy to induce redox events has been employed in the Wittig, Appel, and Staudinger as well as other reactions that are thermodynamically driven by the formation of phosphine oxide, [44–94] we also reported the catalytic Wittig reaction [41] and catalytic asymmetric Staudinger‐aza‐Wittig reaction [95] applying the similar strategy. The initial attempt to conduct this approach in the Mitsunobu reaction was disclosed by O'Brien and co‐workers, however, only one example was shown in the patent (Scheme 10).…”

Section: First “Fully” Redox‐driven Catalytic Mitsunobu Reaction?mentioning

confidence: 79%

Progress of Catalytic Mitsunobu Reaction in the Two Decades

et al. 2023

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An important goal of modern synthetic chemistry is the development of highly efficient and selective processes that minimize the formation of waste, which are desirable for economy and environmental requirements. The classic Mitsunobu reaction has been adopted widely for converting alcohols into numerous functional groups and undergoes an inversion of stereochemistry in SN2 reaction when secondary alcohols are employed. However, the reaction is far from ideal in terms of its environmental impact, requiring stoichiometric amounts of a phosphine (III) and an azodicarboxylate, and producing stoichiometric amounts of hydrazine and phosphine oxide wastes. The first attempt to access the catalytic Mitsunobu reaction dates back to 2006 by Toy's group and since then, several groups including Taniguchi, O'Brien, Aldrich, Denton and their co‐workers have opted for this promising alternative. Generally, the substantial progress has been made in the development of catalytic Mitsunobu reaction involving redox‐driven and redox‐neutral processes. The elegant redox‐driven catalytic system applies either external reductants or oxidants to recycle azo or phosphine reagents, while the preeminent redox‐neutral catalytic system is undergoing the activation step to proceed. This review summarizes the related developments in the recent two decades and presents the future research direction.

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Section: First “Fully” Redox‐driven Catalytic Mitsunobu Reaction?mentioning

confidence: 79%

Progress of Catalytic Mitsunobu Reaction in the Two Decades

et al. 2023

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“…= 66-68 °C; UV-Vis: 227 nm (3.81); IR: ν = 3354w, 3314w, 3275w, 2955vw, 2902vw, 1597vw, 1552w, 1474w, 1434vw, 1410w, 1398w, 1362m, 1321m, 1309m, 1294w, 1235vw, 1211vw, 1180m, 1162s, 1120w, 1098m, 1046m, 1020vw, 982w, 957s, 917m, 894w, 854m, 840m, 820m, 799w, 774m, 704w, 665s, 596m, 571m, 547vs, 495m, 473m, 444w, 413vw, 511w cm −1 ; 1 H NMR:δ = 7.70-7.65 (m, 2H, 2-H, 2′-H), 7.52 (t, J = 5.9 Hz, 1H, NH), 7.45-7.36 (m, 4H, 3-H, 3′-H, NH2), 3.96 (t, J = 6.3 Hz, 2H, 9-H), 2.73 (q, J = 6.8 Hz, 2H, 6-H), 2.38 (s, 3H, 5-H), 1.65-1.55 (m, 2H, 8-H), 1.49-1.39 (m, 2H, 7-H) ppm; 13 Applying GPA: from 3-methylbenzenesulfonyl chloride (500 mg, 2.62 mmol) and 2amino-ethanol (240 mg, 3.93 mmol): 19a (542 mg, 96%); oil; Rf = 0.1 (petrolether/EtOAc, 2:3); UV-Vis: 224 nm (3.92); IR: ν = 3493w, 3274w, 2927w, 2882w, 1601vw, 1478w, 1425w, 1321s, 1303s, 1220w, 1148vs, 1097m, 1087m, 1054s, 999w, 949m, 866w, 785m, 687s, 580vs, 524m, 492w, 459m, 435w cm −1 ; 1 H NMR:δ = 7.63-7.61 (m, 1H, 6-H), 7.61-7.58 (m, 1H, 2-H), 7.52 (t, J = 5.8 Hz, 1H, NH), 7.50-7.42 (m, 2H, 4-H, 5-H), 4.66 (t, J = 5.6 Hz, 1H, OH), 3.37 (q, J = 6.3 Hz, 2H, 9-H), 2.79 (q, J = 6.2 Hz, 2H, 8-H), 2.39 (s, 3H, 7-H) ppm; 13 C NMR:δ = 140.5 (C-1), 138.8 (C-3), 132.9 (C-4), 129.0 (C-5), 126.7 (C-6), 123.6 (C-2), 59.9 (C-9), 45 Applying GPB: from 19a (73 mg, 0.4 mmol): 19b (72 mg, 72%); white solid; Rf = 0.52 (CHCl3/EtOAc, 2:3); m.p. = 36-38 °C; UV-Vis: 224 nm (3.65); IR: ν = 3341m, 3259m, 3100w, 2988w, 1566w, 1473w, 1444w, 1421w, 1389w, 1371vs, 1345m, 1325m, 1303s, 1226w, 1174s, 1172s, 1147vs, 1078m, 1062m, 1001m, 951s, 932s, 905m, 879m, 865w, 837s, 791m, 765m, 701s, 683s, 639s, 591s, 571s, 546vs, 504m, 452m, 429w, 544vs, 526m cm −1 ; 1 H NMR:δ = 7.86 (t, J = 5.9 Hz, 1H, NH), 7.64-7.57 (m, 2H, 2-H, 6-H), 7.53-7.44 (m, 4H, 4-H, 5-H, NH2), 3.99 (t, J = 5.7 Hz, 2H, 9-H), 3.04 (q, J = 5.6 Hz, 2H, 8-H), 2.39 (s, 3H, 7-H) ppm; 13 Applying GPA: from 3-methylbenzenesulfonyl chloride (500 mg, 2.62 mmol) and 3amino-propanol (295 mg, 3.93 mmol): 20a (522 mg, 87%) [114] oil; Rf = 0.09 (petrolether/EtOAc, 2:3); UV-Vis: 224 nm (3.91); IR: ν = 3502w, 3276w, 2947w, 2882w, 1477w, 1423w, 1320m, 1303s, 1222w, 1148vs, 1096m, 1085s, 1068m, 1008w, 998w, 959w, 879w, 787m, 688s, 579vs, 524m, 498w, 463m, 434w cm −1 ; 1 H NMR:δ = 7.62-7.56 (m, 2H, 2-H, 6-H), 7.50-7.41 (m, 3H, 4-H, 5-H, NH), 4.40 (t, J = 5.1 Hz, 1H, OH), 3.40-3.35 (m, 2H, 10-H), 2.78 (q, J = 7.0 Hz, 2H, 8-H), 2.39 (s, 3H, 7-H), 1.52 (p, J = 6.4 Hz, 2H, 9-H) ppm; 13…”

Section: -[(4-methylphenyl)sulfonamido]butyl Sulfamate (14b)mentioning

confidence: 99%

Synthesis and Enzymatic Evaluation of a Small Library of Substituted Phenylsulfonamido-Alkyl Sulfamates towards Carbonic Anhydrase II

Denner,

Heise,

Al-Harrasi

et al. 2024

Molecules

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A small library of 79 substituted phenylsulfonamidoalkyl sulfamates, 1b–79b, was synthesized starting from arylsulfonyl chlorides and amino alcohols with different numbers of methylene groups between the hydroxyl and amino moieties yielding intermediates 1a–79a, followed by the reaction of the latter with sulfamoyl chloride. All compounds were screened for their inhibitory activity on bovine carbonic anhydrase II. Compounds 1a–79a showed no inhibition of the enzyme, in contrast to sulfamates 1b–79b. Thus, the inhibitory potential of compounds 1b–79b towards this enzyme depends on the substituent and the substitution pattern of the phenyl group as well as the length of the spacer. Bulkier substituents in the para position proved to be better for inhibiting CAII than compounds with the same substituent in the meta or ortho position. For many substitution patterns, compounds with shorter spacer lengths were superior to those with long chain spacers. Compounds with shorter spacer lengths performed better than those with longer chain spacers for a variety of substitution patterns. The most active compound held inhibition constant as low as Ki = 0.67 μM (for 49b) and a tert-butyl substituent in para position and acted as a competitive inhibitor of the enzyme.

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“…Related tandem processes allowed us in the past few years to access functionalized cyclobutenes, 9 H -pyrrolo[1,2- a ]indoles, 1,2-dihydroquinolines, and tetrahydropyridines via P III /P V redox cycling . In the present case, the putative mechanism described in Scheme C includes the formation of the zwitterionic species (I), after the addition of phosphine to DAAD.…”

mentioning

confidence: 99%

Fluorinated 2-Azetines: Synthesis, Applications, Biological Tests, and Development of a Catalytic Process

et al. 2023

Self Cite

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An efficient and straightforward phosphine-promoted tandem aza-Michael addition/intramolecular Wittig reaction was developed for the synthesis of polyfunctionalized 2-azetines. After demonstrating that this transformation could be made catalytic in phosphine through in situ reduction of phosphine oxide with phenylsilane, different post-transformation steps have been demonstrated, including an original [2 + 2] photodimerization. Preliminary biological tests highlighted that these fluorinated 1,2-dihydroazete-2,3-dicarboxylates exhibited significant cytotoxicity against the human tumor cell line.

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Phosphine‐Catalyzed Synthesis of Chiral N‐Heterocycles through (Asymmetric) P(III)/P(V) Redox Cycling

Cited by 6 publications

References 66 publications

Progress of Catalytic Mitsunobu Reaction in the Two Decades

Progress of Catalytic Mitsunobu Reaction in the Two Decades

Synthesis and Enzymatic Evaluation of a Small Library of Substituted Phenylsulfonamido-Alkyl Sulfamates towards Carbonic Anhydrase II

Fluorinated 2-Azetines: Synthesis, Applications, Biological Tests, and Development of a Catalytic Process

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