Enantioselective Intramolecular Copper‐Catalyzed Borylacylation

Whyte, Andrew; Burton, Katherine; Zhang, Jingli; Lautens, Mark

doi:10.1002/ange.201808460

Cited by 25 publications

(8 citation statements)

References 68 publications

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“…A total of 14 products were obtained, in which (syn, anti)-1,9-bis(4-chlorophenyl)-3,5,7-trimethylnona-1, 8-diyne-3,5,7-triol (syn,anti-5ad) was unambiguously assigned by X-ray analysis (see the Supporting Information). To improve the stereoselectivity, organometallic catalysts [33][34][35] 40 and Pd(OAc) 2 41 were investigated at −15 °C. In addition, different Lewis acids and Lewis bases were also examined, for instance, Yb(OTf) 3 , La(OTf) 3 , AlCl 3 , t-BuOK, lithium diisopropylamide (LDA), NaH, Py, and 4-(dimethylamino)pyridine (DMAP), but the efforts were unsuccessful (Table 2).…”

Section: Resultsmentioning

confidence: 99%

A one-pot diastereoselective synthesis of 1,3-diols and 1,3,5-triols via cascade reactions of arylalkynyl Grignard reagents with enol esters

Jiao

Zhao

Deng

et al. 2020

Journal of Chemical Research

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An efficient cascade reaction has been developed to synthesize a series of 1,3-diols and 1,3,5-triols via reactions of arylalkynyl Grignard reagents with enol esters. The stereoselectivity of reactions and the molecular configurations of the products were confirmed by nuclear magnetic resonance, X-ray diffraction, and high-performance liquid chromatography analysis. A possible reaction mechanism was analyzed with the results indicating that it proceeded through a 1,2-addition/rearrangement and reverse O-acylation to produce the 1,3-diol and via C-acylation to form the 1,3,5-triol.

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Section: Resultsmentioning

confidence: 99%

A one-pot diastereoselective synthesis of 1,3-diols and 1,3,5-triols via cascade reactions of arylalkynyl Grignard reagents with enol esters

Jiao

Zhao

Deng

et al. 2020

Journal of Chemical Research

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“…Later, in 2018, Lautens and coworkers developed a Cu(I)‐catalyzed intramolecular acylboration reaction using a tethered carbamoyl chloride as the electrophile (Scheme ) . It is notable that the products are enantioenriched 3,3‐disubstituted oxindoles, which are biologically interesting molecules …”

Section: Transition‐metal‐catalyzed Alkene 12‐carboboration Reactionsmentioning

confidence: 99%

Transition‐Metal‐Catalyzed 1,2‐Carboboration of Alkenes: Strategies, Mechanisms, and Stereocontrol

Liu

Gao

Zeng

et al. 2019

Israel Journal of Chemistry

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During the past decade, many research groups have described catalytic methods for 1,2-carboboration, allowing access to structurally complex organoboronates from alkenes. Various transition metals, especially copper, palladium, and nickel, have been widely used in these reactions. This review summarizes advances in this field, with a special focus on the catalytic cycles involved in different metal-catalyzed carboboration reactions, as well as the regio-and stereochemical consequences of the underlying mechanisms. 1,2-Carboboration of other unsaturated systems, such as alkynes and allenes, is outside of the scope of this review. Scheme 1. General depiction of catalyst-controlled 1,2-carboboration. In this scheme and throughout the manuscript, nucleophilic reaction partners are drawn in blue, and electrophilic reaction partners are drawn in red. Scheme 4. Cu(I)-catalyzed borylative radical cyclization. Scheme 5. Cu(I)-catalyzed intramolecular carboboration involving an aldol cyclization. Scheme 6. Cu(I)-catalyzed intramolecular acylboration.Review Isr. J. Chem. 2020, 60, 219 -229 Scheme 7. Cu(I)-catalyzed divergent alkylboration of alkenes. Scheme 8. Cu(I)-catalyzed alkene carboboration with aldehydes as the electrophile. Scheme 9. Cu(I)-catalyzed three-component acylboration. Scheme 10. Cu(I)-catalyzed heteroarylboration of 1,3-dienes.

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“…10−14 In 2018, we disclosed the use of carbamoyl chlorides as acylating electrophiles in the copper-catalyzed borylacylation of styrenes to generate chiral oxindoles (Scheme 1a). 10 More recently, the Mazet 13 and Tao 14 groups concomitantly reported using exogenous isocyanides to generate secondary amides (Scheme 1b). Notably, utilizing internal alkenes has yet to be fully realized yet represents a potentially valuable pathway toward creating amides with two contiguous stereocenters.…”

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confidence: 99%

“…Substrate 1a was the starting point for the investigation, using reaction conditions similar to our previous report. 10 The optimal conditions involve dppe (L1) as the ligand and THF as the solvent (Table 1, entry 1). At room temperature, the 3,4-disubstituted γ-lactam (2a) was isolated in 97% yield as a single diastereomer with syn configuration (Scheme 2).…”

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confidence: 99%