Catalytic asymmetric synthesis of 3,3-disubstituted oxindoles: diazooxindole joins the field

Cao, Zhong‐Yan; Wang, Yuhui; Zeng, Xing‐Ping; Zhou, Jian

doi:10.1016/j.tetlet.2014.01.084

Cited by 129 publications

(29 citation statements)

References 179 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[1][2][3][4] Therefore, spirocyclic oxindole scaffolds have continued to draw attention in recent years. [8][9][10][11][12] Since the pioneering work of Nozaki and Noyori, 13 the transition metal-catalyzed asymmetric cyclopropanation between diazo compounds and alkenes has emerged as a powerful strategy for the synthesis of cyclopropane derivatives. [5][6][7] As a result, great efforts have been directed toward asymmetric construction of these scaffolds.…”

Section: Introductionmentioning

confidence: 99%

Mechanism and stereoselectivity of the Rh(ii)-catalyzed cyclopropanation of diazooxindole: a density functional theory study

2015

View full text Add to dashboard Cite

The mechanism and origin of stereoselectivity of rhodium(II)-catalyzed cyclopropanation reactions with diazooxindole and styrene has been studied using density functional theory calculations. The catalyzed reactions by achiral Rh 2 (OAc) 4 and chiral Rh 2 (S-PTTL) 4 as well as the uncatalyzed model were comparatively studied. The computational results indicate that the cyclopropanation step in both Rh 2 (OAc) 4 and Rh 2 (S-PTTL) 4 models is a single concerted but asynchronous process. The nitrogen extrusion step is found to be the rate-limiting step of the catalytic cycle, whereas the cyclopropanation step is the stereoselectivity-determining step. The diastereomeric ratios (dr) and the enantiomeric excess (ee) values are successfully predicted, which are in good agreement with the experimental values. The high trans-diastereoselectivity might be governed by the p-p interactions between the syn indole ring in carbenoid ligand and the phenyl group in styrene, whereas the good enantioselectivity can be ascribed to the steric interaction between the phenyl ring in styrene and the phthalimido group in the catalyst as well as the aromatic interactions (p-p and CH-p) in the transition states. Additionally, the methodological study using different functionals demonstrated the importance of considering the dispersion interactions in the current reaction systems. This theoretical study will help in understanding the mechanism of the asymmetric cyclopropanations of olefins through carbene-transfer reactions. † Electronic supplementary information (ESI) available: Comparison of different DFT methods (Table S1), calculated relative free energies with and without BSSE correction (Table S2), NBO analysis of TS11a and TS11b (Table S3), natural charge analysis (Tables S4 and S5), energy prole for the uncatalyzed cyclopropanation in Re-face pathway (Fig. S1), comparison between the DFT and X-ray structure of Rh 2 (OAc) 4 (Fig. S2), and other gures and tables, and xyz le giving the Cartesian coordinates for all structures. See Scheme 1 Rh 2 (S-PTTL) 4 catalyzed cyclopropanation of styrene and diazooxindole.Scheme 2 Proposed catalytic cycle for the asymmetric cyclopropanation.57782 | RSC Adv., 2015, 5, 57781-57791This journal is

show abstract

Section: Introductionmentioning

confidence: 99%

Mechanism and stereoselectivity of the Rh(ii)-catalyzed cyclopropanation of diazooxindole: a density functional theory study

2015

View full text Add to dashboard Cite

show abstract

“…Such developments are of interest not only for the possible total synthesis of therapeutically useful spirooxindoles [6][7][8][9][10][11][12][13][14][15], but also for the preparation of synthetic analogs [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] in order to improve our knowledge in structure-activity relationships [12-14, 31, 32]. So-called butenolide functionalized spirooxindoles 1 provide the most interesting subject for synthetic investigations in view of the large and ever increasing number of the members of this family which have furan-2(5H)-one 2 as a building block (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

The Synthesis of New Spirolactones from Substituted Isatins

Sucman¹,

Pogrebnoi²,

Обушак³

et al. 2015

ChemJMold

View full text Add to dashboard Cite

Abstract. Interaction of N-ethyl isatin 3 with dimethyl acetylenedicarboxylate in the presence triphenylphosphine has led to good selectivity of methyl 1'-ethyl-4-methoxy-2',5-dioxo-5H-spiro[furan-2,3'-indoline]-3-carboxylate 4 formation. Similar yields of spirolactones 6,8 were obtained by addition of dimethyl acetylenedicarboxylate to 5-bromo functionalized isatins 5,7. However, reaction of N-butyl isatin 9 resulted in formation of an inseparable mixture of compounds. Treatment of N-benzyl isatin 10 and dimethyl acetylenedicarboxylate with triphenylphosphine proceeded with reduced selectivity of the spirooxindole 11 formation.Keywords: spirolactones, isatins, triphenylphosphine, dimethyl acetylenedicarboxylate. IntroductionThe widespread distribution of butenolides in naturally occurring [1-3] and synthetic bioactive substances strongly motivate an interest for improving the methodology of the selective synthesis of butenolide functionalized spirooxindoles in high yield [4,5]. Such developments are of interest not only for the possible total synthesis of therapeutically useful spirooxindoles [6][7][8][9][10][11][12][13][14][15], but also for the preparation of synthetic analogs [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] in order to improve our knowledge in structure-activity relationships [12-14, 31, 32]. So-called butenolide functionalized spirooxindoles 1 provide the most interesting subject for synthetic investigations in view of the large and ever increasing number of the members of this family which have furan-2(5H)-one 2 as a building block (Scheme 1).

show abstract

“…[9] Their nucleophilic character prompted us to investigate the possibility of ar eductive arylation reaction (Scheme 1d). [12] Although this transformation closely resembles that of the palladium(0)-catalyzed a-arylation reaction, it avoids the use of as trong base for the enolate formation, which eliminates the need for rigorous exclusion of moisture and grants broad functional-group tolerance.H erein, we disclose our findings on the rhodium-catalyzed enantioselective intramolecular reductive arylation reaction that proceeds with high enantiocontrol in an aqueous media. [10] Previously described enantioselective transition-metal-catalyzed methods to access these molecules include palladium-catalyzed a-arylation reactions [11] and aw ide array of domino reactions.…”

mentioning

confidence: 99%

Rhodium‐Catalyzed Enantioselective Reductive Arylation: Convenient Access to 3,3‐Disubstituted Oxindoles

2017

View full text Add to dashboard Cite

Ar hodium-Josiphos(L*) catalyzede nantioselective intramolecular hydroarylation reaction is described. The reductive cyclization of o-bromoaniline-derived acrylamides provides convenient access to 3,3-disubstituted oxindoles in good yields and with excellent enantioselectivity across arange of substrates.W epropose that the key cyclization proceeds via ar hodium(III) intermediate.O verall, this method represents an unusual mode of reactivity for rhodium catalysis and is complementary to palladium(0)-catalyzed a-arylation methods.

show abstract

Catalytic asymmetric synthesis of 3,3-disubstituted oxindoles: diazooxindole joins the field

Cited by 129 publications

References 179 publications

Mechanism and stereoselectivity of the Rh(ii)-catalyzed cyclopropanation of diazooxindole: a density functional theory study

Mechanism and stereoselectivity of the Rh(ii)-catalyzed cyclopropanation of diazooxindole: a density functional theory study

The Synthesis of New Spirolactones from Substituted Isatins

Rhodium‐Catalyzed Enantioselective Reductive Arylation: Convenient Access to 3,3‐Disubstituted Oxindoles

Contact Info

Product

Resources

About