Iron‐Catalyzed Asymmetric Hydrosilylation of 1,1‐Disubstituted Alkenes

Chen, Jianhui; Cheng, Biao; Cao, Meng; Lu, Zhan

doi:10.1002/anie.201411884

Cited by 171 publications

(58 citation statements)

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“…Continuing our pursuit of efficient earth-abundant transition metal catalysis via ligand design [36][37][38][39][40][41][42][43][44][45] ; here, we report the use of unsymmetric NNN tridentate ligands to promote the cobaltcatalyzed radical hydroamination of alkenes via HAT ( Fig. 2d).…”

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confidence: 94%

Ligand-promoted cobalt-catalyzed radical hydroamination of alkenes

Shen

Chen

et al. 2020

Nat Commun

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Highly regio-and enantioselective intermolecular hydroamination of alkenes is a challenging process potentially leading to valuable chiral amines. Hydroamination of alkenes via metalcatalyzed hydrogen atom transfer (HAT) with good regioselectivity and functional group tolerance has been reported, however, high enantioselectivity has not been achieved due to the lack of suitable ligands. Here we report a ligand-promoted cobalt-catalyzed Markovnikovtype selective radical hydroamination of alkenes with diazo compounds. This operationally simple protocol uses unsymmetric NNN-tridentate (UNT) ligand, readily available alkenes and hydrosilanes to construct hydrazones with good functional group tolerance. The hydrazones can undergo nitrogen-nitrogen bond cleavage smoothly to deliver valuable amine derivatives. Additionally, asymmetric intermolecular hydroamination of unactivated aliphatic terminal alkenes using chiral N-imidazolinylphenyl 8-aminoquinoline (IPAQ) ligands has also been achieved to afford chiral amine derivatives with good enantioselectivities.

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confidence: 94%

Ligand-promoted cobalt-catalyzed radical hydroamination of alkenes

Shen

Chen

et al. 2020

Nat Commun

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“…In another context, chiral iron complexes have also been employed to promote asymmetric hydrosilylations of alkenes, providing a direct access to pivotal chiral organosilanes [66]. In 2015, Lu et al described the first highly regio-and enantioselective iron-catalyzed anti-Markonivkov hydrosilylation of 1,1disubstituted aryl alkenes 75 [67]. As shown in Scheme 33, the reaction employed Ph 2 SiH 2 as a silylating agent and was catalyzed at room temperature by 1-5 mol% of tridentate N3 chiral iron complex 76 in the presence of NaBHEt 3 as a reducing agent in toluene or even without solvent.…”

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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“…The in situ activation of more robust Fe(II/III) precursors has emerged as a method to avoid the need to prepare and handle low oxidation‐state species ,. Strongly reducing organometallic reagents such as Grignard reagents,, NaHBEt 3 ,, and activated magnesium are commonly used as activators (Figure , [a]). These reagents are inherently pyrophoric, unstable to both air and moisture, can be incompatible with substrate functionality, and negate the inherent environmental and practical benefits of using an iron (pre‐)catalyst.…”

Section: Figurementioning

confidence: 99%

Amine‐Activated Iron Catalysis: Air‐ and Moisture‐Stable Alkene and Alkyne Hydrofunctionalization

et al. 2016

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As imple alkylamine[ ( iPr) 2 NEt] has been used to activate an air-a nd moisture-stable iron(II) pre-catalyst for alkene and alkyne hydrofunctionalization reactions.T his amine activation has enabled the highly operationallys imple hydrosilylation and hydroborationo fa lkenes and alkynes using just 0.25-2 mol% iron catalyst and 1-25 mol% amine. Significantly,t hese reactions proceedi ne qual yield under both air and inert reactionc onditions.

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Iron‐Catalyzed Asymmetric Hydrosilylation of 1,1‐Disubstituted Alkenes

Cited by 171 publications

References 78 publications

Ligand-promoted cobalt-catalyzed radical hydroamination of alkenes

Ligand-promoted cobalt-catalyzed radical hydroamination of alkenes

Recent developments in enantioselective iron-catalyzed transformations

Amine‐Activated Iron Catalysis: Air‐ and Moisture‐Stable Alkene and Alkyne Hydrofunctionalization

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