Enantioselective Copper-Catalyzed Electrophilic Dearomative Azidation of β-Naphthols

Wang, Chong-Ji; Sun, Jian; Zhou, Wei; Xue, Jing; Ren, Bing-Tao; Zhang, Guangyi; Mei, Yan-Le; Deng, Qing‐Hai

doi:10.1021/acs.orglett.9b02604

Cited by 35 publications

(15 citation statements)

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“…By using a Cu‐catalyst modified with chiral N,N‐ligand 84 , Deng and co‐workers have shown that highly enantioselective dearomatizing azidation reactions are possible (Scheme 27). [57] In this method, hypervalent iodine‐based azide transfer reagent 83 is used and the method requires a carbonyl substituent at C2 of the naphthol. This facilitates two‐point binding of the substrate to the Cu‐center in advance of enolate‐like attack onto the azide electrophile.…”

Section: Discussionmentioning

confidence: 99%

Dearomatizing Amination Reactions

Jing

Farndon

Bower

2021

The Chemical Record

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Dearomatization reactions allow the direct synthesis of structurally complex sp 3 -rich molecules from readily available "flat" precursors. Established dearomatization processes commonly involve the formation of new CÀ C bonds, whereas methods that enable the introduction of CÀ N bonds have received less attention. Because of the privileged position of nitrogen in drug discovery, significant recent methodological efforts have been directed towards addressing this deficiency. Consequently, a variety of new processes are now available that allow the direct preparation of sp 3 -rich amino-containing building blocks and scaffolds. This review gives an overview of CÀ N bond forming dearomatization reactions, particularly with respect to scaffold assembly processes. The discussion gives historical context, but the main focus is on selected methods that have been reported recently.

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Section: Discussionmentioning

confidence: 99%

Dearomatizing Amination Reactions

Jing

Farndon

Bower

2021

The Chemical Record

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“…Afterward, the Sarkar group developed a similar reaction using the reagent system of NaN 3 /phenyl trimethylammonium tribromide (PTAB) under metal-free conditions . An enantioselective version of this transformation using hypervalent iodo azide reagent as azide source was achieved by the Deng group . Remarkably, employing Cu(CH 3 CN) 4 ·PF 6 and a 4,6-dibenzofurandiyl-2,2′-bisoxazolin (dbfox) ligand resulted in the desired enantioenriched α-azido β-naphthalenones in excellent yields with moderate to high enantioselectivities (Scheme ).…”

Section: Azidation Of C–c Multiple Bondsmentioning

confidence: 99%

New Strategies for the Synthesis of Aliphatic Azides

2021

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Aliphatic azides are a versatile class of compounds found in a variety of biologically active pharmaceuticals. These compounds are also recognized as useful precursors for the synthesis of a range of nitrogen-based scaffolds of therapeutic drugs, biologically active compounds, and functional materials. In light of the growing importance of aliphatic azides in both chemical and biological sciences, a vast array of synthetic strategies for the preparation of structurally diverse aliphatic azides have been developed over the past decades. However, to date, this topic has not been the subject of a dedicated review. This review aims to provide a concise overview of modern synthetic strategies to access aliphatic azides that have emerged since 2010. The discussed azidation reactions include (a) azidation of C–C multiple bonds, (b) azidation of C–H bonds, (c) the direct transformation of vinyl azides into other aliphatic azides, and (d) miscellaneous reactions to access aliphatic azides. We critically discuss the synthetic outcomes and the generality and uniqueness of the different mechanistic rationale of each of the selected reactions. The challenges and potential opportunities of the topic are outlined.

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“…For example, it has been shown that chiral iron or copper catalysts can promote highly enantioselective electrophilic azide transfers. [ 27 , 66 ] In these processes, the electrophilic aminating agent is an azide‐containing hypervalent iodine(III) species. These species are often highly unstable; however, it has been shown that safer variants can be developed.…”

Section: α‐Amination Of Carbonyl Compoundsmentioning

confidence: 99%