C–H/C–C Functionalization Approach to N-Fused Heterocycles from Saturated Azacycles

Ham, Jin Su; Park, Bohyun; Son, Mina; Roque, Jose B.; Jurczyk, Justin; Yeung, Charles S.; Baik, Mu‐Hyun; Sarpong, Richmond

doi:10.1021/jacs.0c04278

Cited by 42 publications

(30 citation statements)

References 46 publications

(31 reference statements)

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“…A related strategy was applied to the synthesis of indolizidine derivatives 179 ( Scheme 22 ). In contrast to their previous work where a Pd catalyst was used ( Scheme 21 ), they found that 5 mol% of [Rh(OH)(COD)] 2 in the presence of 15 mol% of Xantphos ligand and K 2 CO 3 could selectively promote the cleavage of the distal C–C bond through the β-carbon elimination process in 180 [ 79 ]. Then, a decarbonylation step would render the chelated complex 182 .…”

Section: Synthetic Methodology Involving C–h Functionalization Alomentioning

confidence: 88%

Recent Advances on Synthetic Methodology Merging C–H Functionalization and C–C Cleavage

Azizollahi

Garcı́a-López

2020

Molecules

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The functionalization of C–H bonds has become a major thread of research in organic synthesis that can be assessed from different angles, for instance depending on the type of catalyst employed or the overall transformation that is carried out. This review compiles recent progress in synthetic methodology that merges the functionalization of C–H bonds along with the cleavage of C–C bonds, either in intra- or intermolecular fashion. The manuscript is organized in two main sections according to the type of substrate in which the cleavage of the C–C bond takes place, basically attending to the scission of strained or unstrained C–C bonds. Furthermore, the related research works have been grouped on the basis of the mechanistic aspects of the different transformations that are carried out, i.e.,: (a) classic transition metal catalysis where organometallic intermediates are involved; (b) processes occurring via radical intermediates generated through the use of radical initiators or photochemically; and (c) reactions that are catalyzed or mediated by suitable Lewis or Brønsted acid or bases, where molecular rearrangements take place. Thus, throughout the review a wide range of synthetic approaches show that the combination of C–H and C–C cleavage in single synthetic operations can serve as a platform to achieve complex molecular skeletons in a straightforward manner, among them interesting carbo- and heterocyclic scaffolds.

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Section: Synthetic Methodology Involving C–h Functionalization Alomentioning

confidence: 88%

Recent Advances on Synthetic Methodology Merging C–H Functionalization and C–C Cleavage

Azizollahi

Garcı́a-López

2020

Molecules

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“…The collaboration between MSD and Berkeley was one key pillar of that strategy, and together with Richmond's lab, we were able to make major inroads in the area of bicyclic amine synthesis and molecular editing," said Dr. Charles Yeung. As part of this collaboration, the Sarpong group (graduate students Justin Jurczyk and Sojung Kim) and scientists at MSD (Dr. Charles Yeung, Dr. Michaelyn Lux, Dr. Colin Lam, and Dr. Donovon Adpressa) worked productively on several projects, including the synthesis of bicyclic amines 5,6 and piperidine peripheral functionalization. 7 Building on insights from their Pd-catalyzed piperidine functionalization research, they reasoned that α-benzoylated piperidine scaffolds could undergo further diversification using the photoactive benzoyl group.…”

Section: Literature Coverage Synformmentioning

confidence: 99%

Synform Issue 2022/1

Zanda¹

2021

Synthesis

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I am delighted to introduce a new year of SYNFORM with an absolutely first-class January issue, packed full of great science, published in top-notch journals. If a good beginning bodes well, it is safe to say that we have a very exciting year ahead. The critical duty of kicking off this season is on the shoulders of Y. Nagata (Japan) who is the protagonist -and past Thieme Chem istry Journals Awardee -of our Young Career Focus interview, which zooms in on robot-assisted synthesis and stereochemical properties of polymers in solution. The first Literature Coverage article covers a recent ground-breaking publication in Science by the group of R. Sarpong (USA) on a photo-mediated ring contraction of saturated heterocycles, such as piperid ines, cyclic ethers and thioethers, which allows for the skeletal editing of complex cyclic organic molecules. The next Literature Coverage article covers another recent Science paper, authored by the group of W. Han (P. R. of China), on a conceptually new approach to the notoriously challenging selective oxidation of phenols, which has been achieved via iron-catalysed non-directed arene C-H hydroxylation, enabled by L-cystinederived ligands inspired by cytochrome P450 enzymes. The fourth and final article of this pyrotechnic issue covers a new approach -developed through a collaboration involving the groups of M. Bradley (UK) and J. Geng (P. R. of China), and published in Nat. Chem.for activating prodrugs using radiotherapy, and specifically X-rays, which holds great promise for future clinical applications.

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“…The paradigm of merging transition metal catalysis with photocatalysis has invoked mechanistic wonders in cross-coupling reactions [14][15][16][17][18][19][20][21][22] . This rede ning of chemistry is forged either by a modulated oxidation state or in situ generation of an excited catalytic species through energy transfer 23 .…”

Section: Main Textmentioning

confidence: 99%

Photoinduced regioselective olefination of arenes at proximal and distal sites

Saha¹,

Guin²,

Ali³

et al. 2020

Preprint

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The Fujiwara-Moritani reaction has had a profound contribution in the emergence of contemporary C-H activation protocols. Despite the applicability of the traditional approach in different fields, the associated reactivity and regioselectivity issues had rendered it redundant. The revival of this exemplary reaction requires the development of a mechanistic paradigm that would have simultaneous control on both the reactivity and regioselectivity. Often high thermal energy required to promote olefination leads to multiple site functionalization. To this aim we established a photoredoxcatalytic system constituting a merger of palladium/organo-photocatalyst that forges oxidative olefination in an explicit regioselective fashion of diverse arenes and heteroarenes. Visible light plays a significant role in executing ‘regio-resolved’ Fuijiwara-Moritani reaction without the requirement of silver salts and thermal energy. The catalytic system is also amenable towards proximal and distal olefination aided by respective directing groups (DGs), which entails the versatility of the protocol in engaging the entire spectrum of C(sp2)-H olefination. Furthermore, streamlining the synthesis of natural products, chiral molecules, drugs and diversification through late-stage functionalizations underscore the importance of this sustainable protocol. The photoinduced attainment of this regioselective transformation is mechanistically established through control reactions, kinetic studies and theoretical calculations.

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C–H/C–C Functionalization Approach to N-Fused Heterocycles from Saturated Azacycles

Cited by 42 publications

References 46 publications

Recent Advances on Synthetic Methodology Merging C–H Functionalization and C–C Cleavage

Recent Advances on Synthetic Methodology Merging C–H Functionalization and C–C Cleavage

Synform Issue 2022/1

Photoinduced regioselective olefination of arenes at proximal and distal sites

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