Iron-catalysed asymmetric carboazidation of styrenes

Ge, Liang; Zhou, Huan; Chiou, Mong‐Feng; Jiang, Hui; Jian, Wujun; Ye, Changqing; Li, Xiaoyan; Zhu, Xiaotao; Xiong, Hai; Li, Yajun; Song, Lijuan; Zhang, Xinhao; Bao, Hongli

doi:10.1038/s41929-020-00551-4

Cited by 79 publications

(57 citation statements)

References 69 publications

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“…Functional groups such as alkyl (4), cyano (8), alkyloxy (13), and trifluoromethyl (7 and 11) are tolerated, as are halides (5, 6, 9, and 10) that can be used subsequently in well-developed cross-coupling reactions. The diene substrates with a terminal C-C triple bond (17), a disubstituted phenyl group (14, 15, and 16), a thienyl group (18), a naphthyl group (19 and 20), and a pyrenyl group (21) can provide the corresponding products with a er value as high as 95:5. A screening of the alkyl diacyl peroxides revealed that not only primary alkyl radicals but secondary alkyl radicals can participate (33) are tolerated.…”

Section: Resultsmentioning

confidence: 99%

“…The two faces of a planar radical or the two invertomers of pyramidal radicals must be recognized and the radical must be rapidly converted into the desired products before undesirable side reactions can take place. Recently, the creation of stereoselective C-C, C-N, C-Br bonds on a radical center has been incrementally realized by Fu [1][2][3][4][5] , Liu [6][7][8][9] , Ready 10 , Reisman 11,12 , and others [13][14][15][16][17][18][19][20] (Fig. 1a), and these breakthroughs have inspired the field, leading to significant progress and discovery of many relevant and useful reactions.…”

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confidence: 99%

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Asymmetric radical carboesterification of dienes

et al. 2021

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The straightforward strategy of building a chiral C-O bond directly on a general carbon radical center is challenging and stereocontrol of the reactions of open-chain hydrocarbon radicals remains a largely unsolved problem. Advance in this elementary step will spur the development of asymmetric radical C-O bond construction. Herein, we report a copper-catalyzed regioselective and enantioselective carboesterification of substituted dienes using alkyl diacyl peroxides as the source of both the carbon and oxygen substituents. The participation of external acids in this reaction substantially extends its applicability and leads to structurally diverse allylic ester products. This work represents the advance in the key elementary reaction of intermolecular enantioselective construction of C-O bond on open-chain hydrocarbon radicals and may lead to the discovery of other asymmetric radical reactions.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Asymmetric radical carboesterification of dienes

et al. 2021

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“…However, these methods are restricted by some drawbacks such as the use of prefunctionalized starting materials. Direct difunctionalization of alkenes has emerged as a powerful strategy in organic synthesis, which has been successfully applied in the conversion of olefins into more structurally diverse 1,2-difunctionalized compounds ( Fu et al., 2017 ; Ge et al., 2020 ; Koike and Akita, 2018 ; McDonald et al., 2011 ; Sauer and Lin, 2018 ; Yin et al., 2016 ). Vicinal hydroxyazidation of alkenes offers a simpler and more convenient approach for preparing 1,2-azidoalcohols.…”

Section: Introductionmentioning

confidence: 99%

Regiodivergent and stereoselective hydroxyazidation of alkenes by biocatalytic cascades

Wan

et al. 2021

iScience

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Summary Asymmetric functionalization of alkenes allows the direct synthesis of a wide range of chiral compounds. Vicinal hydroxyazidation of alkenes provides a desirable path to 1,2-azidoalcohols; however, existing methods are limited by the control of stereoselectivity and regioselectivity. Herein, we describe a dual-enzyme cascade strategy for regiodivergent and stereoselective hydroxyazidation of alkenes, affording various enantiomerically pure 1,2-azidoalcohols. The biocatalytic cascade process is designed by combining styrene monooxygenase-catalyzed asymmetric epoxidation of alkenes and halohydrin dehalogenase-catalyzed regioselective ring opening of epoxides with azide. Additionally, a one-pot chemo-enzymatic route to chiral β -hydroxytriazoles from alkenes is developed via combining the biocatalytic cascades and Cu-catalyzed azide-alkyne cycloaddition.

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“…In 2021, the Bao group followed up on their previous work and developed an asymmetric carboazidation of styrene derivatives 115 ( Scheme 33 ) [ 135 ]. The authors propose the enantioselectivity originates from the diastereoisomeric azido group transfer from the Fe(III) center to the benzylic radical.…”

Section: Reviewmentioning

confidence: 99%

Iron-catalyzed domino coupling reactions of π-systems

Pounder¹,

Tam²

2021

Beilstein J. Org. Chem.

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The development of environmentally benign, inexpensive, and earth-abundant metal catalysts is desirable from both an ecological and economic standpoint. Certainly, in the past couple decades, iron has become a key player in the development of sustainable coupling chemistry and has become an indispensable tool in organic synthesis. Over the last ten years, organic chemistry has witnessed substantial improvements in efficient synthesis because of domino reactions. These protocols are more atom-economic, produce less waste, and demand less time compared to a classical stepwise reaction. Although iron-catalyzed domino reactions require a mindset that differs from the more routine noble-metal, homogenous iron catalysis they bear the chance to enable coupling reactions that rival that of noble-metal-catalysis. This review provides an overview of iron-catalyzed domino coupling reactions of π-systems. The classifications and reactivity paradigms examined should assist readers and provide guidance for the design of novel domino reactions.

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Iron-catalysed asymmetric carboazidation of styrenes

Cited by 79 publications

References 69 publications

Asymmetric radical carboesterification of dienes

Asymmetric radical carboesterification of dienes

Regiodivergent and stereoselective hydroxyazidation of alkenes by biocatalytic cascades

Iron-catalyzed domino coupling reactions of π-systems

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