Iron(<scp>ii</scp>)-catalyzed asymmetric intramolecular olefin aminochlorination using chloride ion

Zhu, Chengliang; Tian, Junshan; Gu, Zhen-yuan; Xing, Guo‐wen; Xu, Hao

doi:10.1039/c5sc00221d

Cited by 62 publications

(26 citation statements)

References 46 publications

(16 reference statements)

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“…Basic tertiary nitrogen centers (35,18,38, and 39) were also tolerated, an important prerequisite for the application of any methodology for the discovery of bioactive compounds. Heterocycles commonly used in drug discovery, such as tetrazole (19), oxetane (20), and purine (38), could be readily used, as could an alkyne (15). Furthermore, aromatic halides (12 and 13), which can serve as handles for further functionalization through cross-coupling, gave the desired product in good yields.…”

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confidence: 99%

“…A derivative of isosorbide (34), a renewable feedstock, as well as several structurally complex terpene derivatives (36,37,40, and 41) were aminochlorinated in good yields. More importantly, nitrogen-based bioactive scaffolds, such as quincoridine (35), prolinol (39), and even unprotected adenine (38), delivered the corresponding aminated products. Such substrates would arguably pose a great challenge to the vast majority of other transition metal-catalyzed amination reactions.…”

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confidence: 99%

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Efficient access to unprotected primary amines by iron-catalyzed aminochlorination of alkenes

Legnani

Prina-Cerai

Delcaillau

et al. 2018

Science

116

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Primary amines are essential constituents of biologically active molecules and versatile intermediates in the synthesis of drugs and agrochemicals. However, their preparation from easily accessible alkenes remains challenging. Here, we report a general strategy to access primary amines from alkenes through an operationally simple iron-catalyzed aminochlorination reaction. A stable hydroxylamine derivative and benign sodium chloride act as the respective nitrogen and chlorine sources. The reaction proceeds at room temperature under air; tolerates a large scope of aliphatic and conjugated alkenes, including densely functionalized substrates; and provides excellent anti-Markovnikov regioselectivity with respect to the amino group. The reactivity of the 2-chloroalkylamine products, an understudied class of amphoteric molecules, enables facile access to linear or branched aliphatic amines, aziridines, aminonitriles, azido amines, and homoallylic amines.

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confidence: 99%

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confidence: 99%

Efficient access to unprotected primary amines by iron-catalyzed aminochlorination of alkenes

Legnani

Prina-Cerai

Delcaillau

et al. 2018

Science

116

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“…537 The racemic version employed phenanthroline as the ligand, whereas the enantioselective variant required the use of the bisoxazole ligand 568. Both forms of the reaction use Fe(NTf) 2 and TBAC as the Fe and chloride source, respectively, and were found to proceed efficiently at or below 0°C.…”

Section: Fe- Ru- and V-catalyzed Reactionsmentioning

confidence: 99%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

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The high utility of halogenated organic compounds has prompted the development of a vast number of transformations which install the carbon-halogen motif. Traditional routes to these building blocks have commonly involved multiple steps, harsh reaction conditions, and the use of stoichiometric and/or toxic reagents. In this regard, using transition metals to catalyze the synthesis of organohalides has become a mature field in itself, and applying these technologies has allowed for a decrease in the production of waste, higher levels of regio- and stereoselectivity, and the ability to produce enantioenriched target compounds. Furthermore, transition metals offer the distinct advantage of possessing a diverse spectrum of mechanistic possibilities which translate to the capability to apply new substrate classes and afford novel and difficult-to-access structures. This Review provides comprehensive coverage of modern transition metal-catalyzed syntheses of organohalides via a diverse array of mechanisms. Attention is given to the seminal stoichiometric organometallic studies which led to the corresponding catalytic processes being realized. By breaking this field down into the synthesis of aryl, vinyl, and alkyl halides, it becomes clear which methods have surfaced as most favored for each individual class. In general, a pronounced shift toward the use of C-H bonds as key functional groups, in addition to methods which proceed by catalytic, radical-based mechanisms has occurred. Although always evolving, this field appears to be heading in the direction of using starting materials with a significantly lower degree of prefunctionalization in addition to less expensive and abundant metal catalysts.

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“…Especially, asymmetric aminochlorination reactions of alkenes are still very rare. To address this issue, Xu et al recently developed an iron-catalyzed diastereo-and enantioselective intramolecular aminochlorination of alkenes 52 with tetra-n-butylammonium chloride (TBAC) [60]. As shown in Scheme 26, the process was cat-alyzed by a chiral iron catalyst in situ generated from 15 mol% of Fe (NTf 2 ) 2 and the same quantity of chiral bisoxazoline 53 in chloroform at À60°C.…”

Section: Additions To Alkenesmentioning

confidence: 99%

“…For example, the intramolecular chloroetherification of a variety of activated olefins 62 with p-NsNCl 2 as a chlorine source was optimally catalyzed by 5 mol% of a chiral iron catalyst Scheme 26. Intramolecular aminochlorination of alkenes [60].…”

Section: Additions To Alkenesmentioning

confidence: 99%

Recent developments in enantioselective iron-catalyzed transformations

Pellissier

2019

Coordination Chemistry Reviews

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Scheme 2. Chiral iron catalysts described by Morris, Gao and Mezzetti groups [13,14,16]. Scheme 3. Transfer hydrogenation of alkyl aryl ketones catalyzed by chiral (NH) 2 P 2 macrocyclic iron complexes [17]. Scheme 4. Transfer hydrogenation of alkyl aryl ketones and a phosphinyl imine catalyzed by chiral (NH) 2 P 2 macrocyclic iron complexes [18]. Scheme 5. Transfer hydrogenation of benzyls without base additive [19]. Scheme 8. Hydrogenation of alkyl aryl ketones catalyzed by an iron catalyst derived from a chiral PNP' ligand [29]. Scheme 9. Hydrogenation of alkyl aryl ketones catalyzed by an iron catalyst derived from a chiral monohydride unsymmetrical PNHP' pincer ligand [30]. Scheme 10. Hydrogenation of ketones catalyzed by a chiral cyclopentadienone iron tricarbonyl complex [31]. Scheme 11. Hydrogenation of para-methoxyacetophenone catalyzed by a chiral cyclopentadienone iron tricarbonyl complex embedded in streptavidin [32]. Scheme 14. Hydrosilylation of alkyl aryl ketones catalyzed by a chiral iminopyridine-oxazoline iron complex [41]. Scheme 15. Hydrosilylation of para-phenyl acetophenone catalyzed by a chiral bis(oxazolinyl)phenyl iron complex [42]. Scheme 58. Synthesis of esomeprazole through sulfoxidation [104]. Scheme 59. CAH Alkylation of indoles with aromatic alkenes [105].

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Iron(ii)-catalyzed asymmetric intramolecular olefin aminochlorination using chloride ion

Cited by 62 publications

References 46 publications

Efficient access to unprotected primary amines by iron-catalyzed aminochlorination of alkenes

Efficient access to unprotected primary amines by iron-catalyzed aminochlorination of alkenes

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Recent developments in enantioselective iron-catalyzed transformations

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