Enantioselective Synthesis of Aminodiols by Sequential Rhodium‐Catalysed Oxyamination/Kinetic Resolution: Expanding the Substrate Scope of Amidine‐Based Catalysis

Guasch, Joan; Giménez‐Nueno, Irene; Funes‐Ardoiz, Ignacio; Bernús, Miguel; Matheu, M. Isabel; Maseras, Feliu; Castillón, Sergio; Dı́az, Yolanda

doi:10.1002/chem.201705670

Cited by 16 publications

(6 citation statements)

References 74 publications

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“…R f = 0.12 (30% Et 2 O in pentane); mp = 48–51 °C; IR (film)/cm –1 3425, 3307, 3280, 3211, 2952, 1675, 1647, 1607, 1405, 1328, 1062, 865, 702, 634, 563; 1 H NMR (400 MHz, CDCl 3 ) δ 4.93 (br s, 2H, NH 2 ), 4.69 (d, J = 2.5 Hz, 2H, CH 2 ), 2.50 (t, J = 2.5 Hz, 1H, CCH); 13 C NMR (101 MHz, CDCl 3 ) δ 155.8 (CO), 77.9 ( C CH), 74.8 (C C H), 52.7 (CH 2 ). Analytical data (NMR and IR) in agreement with those reported in the literature …”

Section: Methodssupporting

confidence: 88%

Synthesis of Sulfoximine Propargyl Carbamates under Improved Conditions for Rhodium Catalyzed Carbamate Transfer to Sulfoxides

et al. 2022

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Sulfoximines provide aza-analogues of sulfones, with potentially improved properties for medicinal chemistry. The sulfoximine nitrogen also provides an additional vector for the inclusion of other functionality. Here, we report improved conditions for rhodium catalyzed synthesis of sulfoximine (and sulfilimine) carbamates, especially for previously low-yielding carbamates containing π-functionality. Notably we report the preparation of propargyl sulfoximine carbamates to provide an alkyne as a potential click handle. Using Rh 2 (esp) 2 as catalyst and a DOE optimization approach provided considerably increased yields.

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Section: Methodssupporting

confidence: 88%

Synthesis of Sulfoximine Propargyl Carbamates under Improved Conditions for Rhodium Catalyzed Carbamate Transfer to Sulfoxides

et al. 2022

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“…Considering the potential importance of dienyl carbamates in the synthesis of natural products, the carbamoylation/rearrangement/hydrolysis sequence was also extended to other substrates, such as C3-alkenyl-substituted allylic alcohols 5 . The results indicated in Table led to similar conclusions regarding the electronic effects that promote the rearrangement.…”

Section: Resultsmentioning

confidence: 99%

1,3-Dioxa-[3,3]-sigmatropic Oxo-Rearrangement of Substituted Allylic Carbamates: Scope and Mechanistic Studies

et al. 2018

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An unexpected 1,3-dioxa-[3,3]-sigmatropic rearrangement during the treatment of aryl-and alkenyl-substituted allylic alcohols with activated isocyanates is reported. The reorganization of bonds is highly dependent on the electron density of the aromatic ring and the nature of isocyanate used. This metal-free tandem reaction from branched allyl alcohols initiated by a carbamoylation reaction and followed by a sigmatropic rearrangement thus offers a new access to (E)-cinnamyl and conjugated (E,E)-diene carbamates, such as N-acyl and N-sulfonyl derivatives. A computational study was conducted in order to rationalize this phenomenon, and a rearrangement progress kinetic analysis was performed.

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“…In particular, sphingolipids have been reported to be involved in cell recognition and signal transduction and exhibit prominent antitumor, immune‐modulatory and immunosuppressive activities. [4] In addition, many synthetic compounds have 3‐amino‐1,2‐diol moieties in their backbones, including the antitumor agent aminocyclopentitol pactamycin, the proteasome inhibitor TMC‐95 A, the immunosuppressant antibiotic myriocin, riboflavin (vitamin B2) and the hydrogenase coenzyme F420. [5] Besides being of pharmacological interest, 3‐amino‐1,2‐diols have proven to be excellent building blocks for the synthesis of various heterocyclic compounds such as 1,3‐oxazine,[ 6 , 7 ] 1,3‐thiazine [8] and pyrimidines.…”

Section: Introductionmentioning

confidence: 99%

Antiproliferative Activity of (−)‐Isopulegol‐based 1,3‐Oxazine, 1,3‐Thiazine and 2,4‐Diaminopyrimidine Derivatives

Bamou

Tayeb

et al. 2022

ChemistryOpen

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A series of novel heterocyclic structures, namely 1,3‐oxazines, 1,3‐thiazines and 2,4‐diaminopyrimidines, were designed and synthesised. The bioassay tests demonstrated that, among these analogues, 2,4‐diaminopyridine derivatives showed significant antiproliferative activity against different human cancer cell lines (A2780, SiHa, HeLa, MCF‐7 and MDA‐MB‐231). Pyrimidines substituted with N 2 ‐( p ‐trifluoromethyl)aniline, in particular, displayed a potent inhibitory effect on the growth of cancer cells. Structure–activity relationships were also studied from the aspects of stereochemistry on the aminodiol moiety as well as exploring the effects of substituents on the pyrimidine scaffold.

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Enantioselective Synthesis of Aminodiols by Sequential Rhodium‐Catalysed Oxyamination/Kinetic Resolution: Expanding the Substrate Scope of Amidine‐Based Catalysis

Cited by 16 publications

References 74 publications

Synthesis of Sulfoximine Propargyl Carbamates under Improved Conditions for Rhodium Catalyzed Carbamate Transfer to Sulfoxides

Synthesis of Sulfoximine Propargyl Carbamates under Improved Conditions for Rhodium Catalyzed Carbamate Transfer to Sulfoxides

1,3-Dioxa-[3,3]-sigmatropic Oxo-Rearrangement of Substituted Allylic Carbamates: Scope and Mechanistic Studies

Antiproliferative Activity of (−)‐Isopulegol‐based 1,3‐Oxazine, 1,3‐Thiazine and 2,4‐Diaminopyrimidine Derivatives

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