Gold-Catalyzed Cycloisomerization of Pyridine-Bridged 1,8-Diynes: An Expedient Access to Luminescent Cycl[3.2.2]azines

Chintawar, Chetan C.; Mane, Manoj V.; Tathe, Akash G.; Biswas, Suprakash; Patil, Nitin T.

doi:10.1021/acs.orglett.9b02677

Cited by 27 publications

(18 citation statements)

References 85 publications

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“…On a similar note, computational as well as experimental studies considering the two main possible mechanistic pathways namely Path B and Path C , were reported by Patil and co‐workers in 2019 (Scheme 11). [29] The pyridino‐alkyne substrate 43 under gold‐catalysis generates a gold carbene species 45 which upon nucleophilic attack from the pendant alkyne delivers a β‐gold vinyl cation 46 . Later, this β‐gold vinyl cation 46 could either undergo: a) cyclopropenation/cycloreversion pathway ( Path C ) to sponsor α‐cyclizino gold‐carbene intermediate 48 which then would afford product 44 after oxidation; or b) 46 could directly be intercepted by water molecule followed by its oxidation to afford the final product 44 .…”

Section: Reactions Of Gold Carbene With Alkyne: the Mechanistic Premisementioning

confidence: 99%

Non‐Canonical Reactivity of Gold Carbene with Alkyne: An Overview of the Mechanistic Premise

Sancheti

Patil

2021

Eur J Org Chem

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The unique nature of gold carbene and its synchronous counterpart gold‐stabilized carbocation, is mainly responsible for the non‐canonical reactivity profile that it demonstrates in comparison to any other transition metal carbene. Being an important subset to this class, reactions of gold carbene with alkyne sponsor products far more diverse than cyclopropenation as canonically expected in case of other transition metal carbenes. These gold‐catalyzed reactions have largely been proposed to follow either a [1,n]‐carbene transfer process or an alternate pathway involving a direct interception of the β‐gold vinyl cation with a nucleophile at the cationic carbon. Despite of a clear distinction in structure, bonding and energy of a vinyl gold carbene and β‐gold vinyl cation; they have been found to exhibit identical reactivities like cyclopropenation, C(sp2)–H insertion, etc. making it extremely difficult to “experimentally” investigate and validate a mechanistic pathway. It is because of lack of conclusive experimental evidence, in addition to the limited number of detailed computational studies, that multiple pathways have been proposed simultaneously to rationalize the product formation. As an effort to shed light on the mechanisms of these reactions, herein, documentation of these reactions with a focus on their mechanistic premise has been presented.

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Section: Reactions Of Gold Carbene With Alkyne: the Mechanistic Premisementioning

confidence: 99%

Non‐Canonical Reactivity of Gold Carbene with Alkyne: An Overview of the Mechanistic Premise

Sancheti

Patil

2021

Eur J Org Chem

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“…With this aforementioned strategy, our endeavour towards the optimization of the reaction led us to a gold-catalyzed cycloisomerization reaction of pyridine-bridged 1,8-diynes 49 to afford cycl [3.2.2] azines 54 (Scheme 20). [44] In order to gain a better understanding of the operating mechanism, we performed few control experiments (Scheme 21). Firstly, to inspect the role of DMSO as a source of oxygen in the product, we have used the analogous diphenyl sulfoxide (Ph 2 SO) in the reaction medium in place of DMSO.…”

Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

“…With this aforementioned strategy, our endeavour towards the optimization of the reaction led us to a gold‐catalyzed cycloisomerization reaction of pyridine‐bridged 1,8‐diynes 49 to afford cycl[3.2.2] azines 54 (Scheme 20). [44] …”

Section: 2‐aminofunctionalization Reactions Of Pyridino‐alkynesmentioning

confidence: 99%

1,2‐Aminofunctionalization Reactions of Pyridino‐Alkynes via Carbophilic Activation

Paroi

Sancheti

Patil

2021

The Chemical Record

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Transition metal-catalyzed 1,2-difunctionalization reactions of alkynes have emerged as a powerful tool to forge carbon-carbon and carbon-heteroatom bonds for the rapid synthesis of polyfunctionalized molecular scaffolds. In this regard, our group has persistently been developing transition metal-mediated 1,2-aminofunctionalization reactions of alkynes through a rationally designed pyridino-alkyne core by utilizing the carbophilic activation strategy. In this account, we present an array of such 1,2-aminofunctionalization reactions which have been successfully executed on this core to afford important polycyclic frameworks such as functionalized quinalizinones, pyridinium oxazole dyads (PODs), N-doped polycyclic aromatic hydrocarbons (PAHs), N-doped spiro-PAHs. Additionally, the synthesis of phosphine ligated gold complexes bearing pyrido-isoquinoline scaffold from the pyridino-alkynes will be discussed briefly.

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“…Thus, this efficient synthetic route paves the way to develop novel N-PAHs containing central nitrogen atoms. 67 As mentioned above, compound 5 can be achieved through the [3+2] cycloaddition of PAMY and DMAD. Interestingly, dimerized compound 18 was also generated in the solution of PAMY without DMAD in only 3% yield (Scheme 2).…”

Section: Account Syn Lettmentioning

confidence: 99%

Bottom-Up Synthesis of Nitrogen-Doped Polycyclic Aromatic Hydrocarbons

Liu

Feng

2019

Synlett

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Bottom-up organic synthesis serves as an efficient method to provide atomically precise heteroatom-doped polycyclic aromatic hydrocarbons (PAHs) with not only well-defined size and edge structures but also specific concentrations and positions of the heteroatoms. We provide a plenary account of the preparation of nitrogen-doped PAHs (N-PAHs) through 1,3-dipolar cycloaddition between different dipolarophiles, as well as pyrazine-type N-doped diaza-hexa-peri-hexabenzocoronene (diaza-HBC). Additionally, we present the synthesis of a class of helical N-charged PAHs, including one charged aza[5]helicene and two charged aza[4]helicenes. Moreover, the bottom-up organic synthesis strategy is further extended to the construction of novel nitrogen-boron-nitrogen (NBN)-containing PAHs. Finally, we discuss the synthesis of four-coordinate boron chromophores containing 6,12,18-tris(alkyl amine)-5,11,17-triazatrinaphthylene derivative ligands.1 Introduction2 Nitrogen-Doped PAHs Based on Dibenzo-9a-azaphenalene (DBAP)3 Cationic Nitrogen-Doped Helical PAHs4 Nitrogen–Boron–Nitrogen-Doped PAHs5 Conclusion and Outlook

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Gold-Catalyzed Cycloisomerization of Pyridine-Bridged 1,8-Diynes: An Expedient Access to Luminescent Cycl[3.2.2]azines

Cited by 27 publications

References 85 publications

Non‐Canonical Reactivity of Gold Carbene with Alkyne: An Overview of the Mechanistic Premise

Non‐Canonical Reactivity of Gold Carbene with Alkyne: An Overview of the Mechanistic Premise

1,2‐Aminofunctionalization Reactions of Pyridino‐Alkynes via Carbophilic Activation

Bottom-Up Synthesis of Nitrogen-Doped Polycyclic Aromatic Hydrocarbons

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