Molybdenum(II)-Catalyzed Allylation of Electron-Rich Aromatics and Heteroaromatics

Malkov, Andrei V.; Davis, Stuart L.; Baxendale, Ian R.; Mitchell, William L.; Kočovský, Pavel

doi:10.1021/jo982178y

Cited by 140 publications

(70 citation statements)

References 29 publications

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“…Stoichiometric amounts of copper metal and copper(II) perchlorate also promote the o-allylation 123 . Molybdenum complexes [Mo(CO) 4 Br 2 ] 2 or Mo(CO) 3 (CH 3 CN) 2 (SnCl 3 )Cl catalyze allylation of phenol with allyl acetate, and (acac) 2 Mo(SbF 6 ) 2 allyl alcohol, in which the formation of a π-allyl molybdenum complex is proposed 124,125 . Treatment of allyl alcohols with Brønsted acids in general provides chromans, for which two mechanisms are suggested: (i) initial O-allylation followed by cyclization, and (ii) initial C-allylation 126 -128 .…”

Section: C-alkylation: Bond Formation With Sp 3 Carbonmentioning

confidence: 99%

Synthetic Uses of Phenols

Yamaguchi

2009

Patai's Chemistry of Functional Groups

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Section: C-alkylation: Bond Formation With Sp 3 Carbonmentioning

confidence: 99%

Synthetic Uses of Phenols

Yamaguchi

2009

Patai's Chemistry of Functional Groups

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“…After an extensive reading of the literature we were surprised to realize that, despite the fact that allylation of indoles is a valuable method to prepare important molecules, only a few examples of mild allylic substitution have been reported and none of them are systematically 55 We then decided to explore the palladium-catalyzed allylation of indoles, aware of the fact that we would face the same problems of regiochemistry with respect to attack at the N-1 or C-3 position of the heteroaromatic system.…”

Section: Scheme 15mentioning

confidence: 99%

A Journey Across Recent Advances in Catalytic and Stereoselective Alkylation of Indoles

Bandini¹,

Melloni²,

Tommasi³

et al. 2005

Synlett

371

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In this Account our recent results in relation to the catalytic and stereoselective Friedel-Crafts (FC) alkylation of indoles are described. Over the last decade, remarkable efforts have been devoted towards the replacement of the primal approaches with new more efficient, reliable, and environmentally benign strategies for the functionalization of indoles. Moreover, the emerging area of catalytic asymmetric FC processes is addressed and some examples of enantioselective alkylations of indoles via 1,4-addition to a,b-unsaturated systems and asymmetric ring-opening reaction of aromatic epoxides are described.

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“…The reaction proceeded smoothly for the carbocyclic ring formation. Good to excellent yields and excellent ee values were obtained for the allylic dearomatization reaction of 1 f-j, varying substituents on 2,6-positions of the phenol and ester groups in the substrates (75-95 % yields, 85-97 % ee; Table 2, entries [6][7][8][9][10]. Notably, when substrate 1 k was used, two stereogenic centers were generated.…”

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confidence: 95%

Iridium‐Catalyzed Intramolecular Asymmetric Allylic Dearomatization of Phenols

et al. 2011

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Dearomatization reactions provide the most direct synthesis of ring systems starting from readily available aromatic compounds.[1] The combination of a dearomatization reaction with asymmetric synthesis would lead to the enantioselective construction of carbocyclic and heterocyclic derivatives. [2] Despite progress in this area, the reported methods have so far focused on a stepwise protocol, which involves the dearomatization process and a subsequent asymmetric reaction.[3] The direct asymmetric dearomatization reaction where the dearomatization and asymmetric catalysis occur in one step is highly desirable but very challenging. [4] As part of our recent studies on iridium-catalyzed allylic substitution reactions, [5][6][7] we found that iridium-catalyzed intramolecular asymmetric allylic alkylation of indole provided enantioenriched spiroindolenine compounds. [8] Phenols are cheap and abundant chemicals widely used in organic synthesis. Transition-metal-catalyzed allylic alkylation reactions of phenols generally proceeds as O allylation [9] with limited examples of C allylation. [9c, 10] Despite the challenges of chemo-, regio-, and enantio-selectivity, we recently envisaged that phenols might function as carbon nucleophiles in the iridium-catalyzed intramolecular allylic dearomatization reactions (Scheme 1). This protocol would provide a direct access to enantiopure spirocyclohexadienones, which serve as a popular structural core in numerous biologically interesting natural products and pharmaceuticals. Scheme 1. Iridium-catalyzed asymmetric allylic dearomatization of phenols. cod = cycloocta-l,5-diene. ,8-diazabicyclo[5.4.0]undec-7-ene, DIEA = N,N-diisopropylethylamine, DMAP = 4-dimethylaminopyridine, DME = 1,2-dimethoxyethane, HMDS

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Molybdenum(II)-Catalyzed Allylation of Electron-Rich Aromatics and Heteroaromatics

Cited by 140 publications

References 29 publications

Synthetic Uses of Phenols

Synthetic Uses of Phenols

A Journey Across Recent Advances in Catalytic and Stereoselective Alkylation of Indoles

Iridium‐Catalyzed Intramolecular Asymmetric Allylic Dearomatization of Phenols

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