Divergent Iron‐Catalyzed Coupling of <i>O</i>‐Acyloximes with Silyl Enol Ethers

Yang, Haibin; Selander, Nicklas

doi:10.1002/chem.201605636

Cited by 172 publications

(75 citation statements)

References 97 publications

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“…In 2016, the group of Selander reported a C−C bond cleavage via the formation of an iminyl radical, where cyclobutanone‐derived O‐acyl oximes underwent a selective fragmentation process catalysed by Fe II complexes. The first example using Cu complexes as a catalyst was reported in 2017 by Zhao and Shi .…”

Section: Deconstructive Functionalization Of Cycloketone Oximes Derivmentioning

confidence: 99%

Radical‐Promoted C−C Bond Cleavage: A Deconstructive Approach for Selective Functionalization

Morcillo

2019

Angew Chem Int Ed

186

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Just as “Deconstructivism” appeared as a novel movement in architecture in the 1980s, deconstructive approaches have recently emerged as excellent strategies for scaffold hopping modifications in chemistry. The deconstruction and functionalization of cyclic molecules mainly involves the cleavage of the carbon–carbon (C−C) bond followed by the construction of new bonds. The cleavage of inert C−C single bonds, especially in unstrained cycles, and their subsequent functionalization is still one of the most sought‐after challenges in chemistry. In this vein, radical‐mediated strategies provide an excellent approach for achieving this aim. This minireview is an outline of the history of homolytic cleavage and highlights the recent advances in exploring new chemical space by deconstructive functionalization.

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Section: Deconstructive Functionalization Of Cycloketone Oximes Derivmentioning

confidence: 99%

Radical‐Promoted C−C Bond Cleavage: A Deconstructive Approach for Selective Functionalization

Morcillo

2019

Angew Chem Int Ed

186

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“…In this context, redox-active acyclic 15 and cyclic 16 oxime derivatives, pioneered by Forrester and Zard, respectively, have been demonstrated to be versatile precursors of iminyl radicals under either oxidative or reductive conditions. Depending on the structure of oximes, the iminyl radicals can evolve to a carbon radical through either β-scission [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] or 1,5hydrogen atom transfer (1,5-HAT) process [33][34][35][36][37][38][39] . The resulting carbon radicals can then be trapped by radical acceptors, affording remote C(sp 3 ) functionalized alkylnitriles and ketones.…”

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confidence: 99%

Functionalization of remote C(sp3)-H bonds enabled by copper-catalyzed coupling of O-acyloximes with terminal alkynes

Torres‐Ochoa

Wang

et al. 2020

Nat Commun

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Transition metal catalyzed Sonogashira cross-coupling of terminal alkynes with aryl(vinyl) (pseudo)halides has been successfully extended to alkyl halides for the synthesis of functionalized internal alkynes. The direct alkynylation of remote unfunctionalized sp 3 carbon by terminal alkynes remains difficult to realize. We report herein an approach to this synthetic challenge by developing two catalytic remote sp 3 carbon alkynylation protocols. In the presence of a catalytic amount of Cu(I) salt and a tridentate ligand (tBu 3-terpyridine), O-acyloximes derived from cycloalkanones and acyclic ketones are efficiently coupled with terminal alkynes to afford a variety of γand δ-alkynyl nitriles and γ-alkynyl ketones, respectively. These reactions proceed through a domino sequence involving copper-catalyzed reductive generation of iminyl radical followed by radical translocation via either β-scission or 1,5hydrogen atom transfer (1,5-HAT) and copper-catalyzed alkynylation of the resulting translocated carbon radicals. The protocols are applicable to complex natural products.

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“…Recent reports by Selander, Shi, and Zhou have advanced the state of the art by enabling iminyl radical fragmentations in the absence of hydrogen atom donors. The alkyl radicals are trapped by alkenes, forging new C−C bonds in the adducts (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Functionalized Nitriles by Microwave‐Promoted Fragmentations of Cyclic Iminyl Radicals

Jackman

Bohman

et al. 2017

Chemistry A European J

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The synthesis of functionalized nitriles via microwave-promoted radical fragmentations of cyclic O-phenyl oxime ethers is reported. A variety of radical traps can be employed, permitting the generation of diverse adducts via C-O, C-C, C-N, or C-X bond formation. Other salient features include a simple and practical protocol, very short reaction times, and the avoidance of metal catalysts and toxic cyanide reagents. The utility of this method is demonstrated by the ring-distortion of a steroid-derived substrate.

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Divergent Iron‐Catalyzed Coupling of O‐Acyloximes with Silyl Enol Ethers

Cited by 172 publications

References 97 publications

Radical‐Promoted C−C Bond Cleavage: A Deconstructive Approach for Selective Functionalization

Radical‐Promoted C−C Bond Cleavage: A Deconstructive Approach for Selective Functionalization

Functionalization of remote C(sp3)-H bonds enabled by copper-catalyzed coupling of O-acyloximes with terminal alkynes

Synthesis of Functionalized Nitriles by Microwave‐Promoted Fragmentations of Cyclic Iminyl Radicals

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