Li<sup>+</sup>‐Mediated BC Cross‐Coupling

Olid, David; Viñas, Clara; Teixidor, Francesç

doi:10.1002/chem.201201881

Cited by 12 publications

(8 citation statements)

References 41 publications

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“…The low yield resulted from the formation of 3-nBu-o-C 2 B 10 H 11 , which was generated from the nucleophilic attack of nBuLi. [14] When the non-nucleophilic base lithium diisopropylamide (LDA) was used, 3 a was obtained in 72 % yield (entry 2). Other less-nucleophilic bases gave relatively lower yields (entries 3-5).…”

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confidence: 99%

1,3‐Dehydro‐o‐Carborane: Generation and Reaction with Arenes

2014

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Like the importance of benzyne, witnessed in modern arene chemistry for decades, 1,2-dehydro-o-carborane (o-carboryne), a three-dimensional relative of benzyne, has been used as a synthon for generating a wide range of cage, carbon-functionalized carboranes over the past 20 years. However, the selective B functionalization of the cage still represents a challenging task. Disclosed herein is the first example of 1,3-dehydro-o-carborane featuring a cage C-B bond having multiple bonding characters, and is successfully generated by treatment of 3-diazonium-o-carborane tetrafluoroborate with non-nucleophilic bases. This presents a new methodology for simultaneous functionalization of both cage carbon and boron vertices.

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confidence: 99%

1,3‐Dehydro‐o‐Carborane: Generation and Reaction with Arenes

2014

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“…To test our hypothesis, a benzene suspension of 1 was treated with 1 equivalent of n BuLi at room temperature for 10 minutes to give the expected [4+2] cycloaddition product 3 a in 38 % yield upon isolation (entry 1, Table 1). The low yield resulted from the formation of 3‐ n Bu‐ o ‐C 2 B 10 H 11 , which was generated from the nucleophilic attack of n BuLi 14. When the non‐nucleophilic base lithium diisopropylamide (LDA) was used, 3 a was obtained in 72 % yield (entry 2).…”

Section: Methodsmentioning

confidence: 99%

A Domino Approach to the Enantioselective Total Syntheses of Blennolide C and Gonytolide C

Tietze

Jackenkroll

Hierold

et al. 2014

Chemistry A European J

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The first enantioselective total syntheses of the tetrahydroxanthenone (-)-blennolide C (ent-4) and related γ-lactonyl chromanone (-)-gonytolide C (ent-3) are reported. Key to the syntheses is an enantioselective domino-Wacker/carbonylation/methoxylation reaction to set up the stereocentre at C-4a. Various chiral BOXAX ligands were investigated, including novel (S,S)-iBu-BOXAX, and allowed access to chromane 8 in an excellent enantioselectivity of 99 %. The second stereocentre at C-4 was established employing a diastereoselective Sharpless dihydroxylation. An extensive survey of (DHQ)- and (DHQD)-based ligands enabled the preparation of both the anti-isomer 14 a and the syn-isomer 14 b in very good to reasonable selectivities of 13.7:1 and 1:3.7, respectively. While 14 a was further converted to ent-3 and ent-4, 14 b was elaborated to syn-acid 25 and 2'-epi-gonytolide C 28.

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“…Noteworthy was the selective arylation of the B(8) and B(10) vertices when using phenylmagnesium bromide as a cross-coupling partner. 101 This selectivity was attributed to the steric bulk of the phenyl substituents which may have prevented functionalization of the more sterically hindered B(9) and B(12) vertices. Similar steric restrictions were observed for the Pd-catalyzed cross-coupling of the hexaiodo monocarborane anion, [1-Ph-7,8,9,10,11,12-I 5 -CB 11 H 5 ] − , where cross-coupling occurred at the less sterically congested B(7–11) positions, but not at the B(12) position, to yield [1-Ph-7,8,9,10,11-(tolyl) 5 -12-I-CB 11 H 5 ] − .…”

Section: Mechanistic Considerations Of Metal-catalyzed Polyhedral Borane Cross-couplingmentioning

confidence: 99%

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

2019

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Over the past several decades, metal-catalyzed cross-coupling has emerged as a very powerful strategy to functionalize carbon-based molecules. More recently, some of the cross-coupling methodologies have been adapted to inorganic compounds including boron-rich clusters. The development of this chemistry relies on the ability to synthesize halogenated boron-rich clusters which can serve as electrophilic cross-coupling partners with nucleophilic substrates in the presence of a metal catalyst. While the cross-coupling chemistry with boron-clusters is conceptually reminiscent to that of its hydrocarbon counterparts, several key aspects including the spheroidal bulk of clusters, and the distinct nature of boron-halogen / boron-heteroatom bonds make this chemistry unique. The utility of metal-catalyzed cross-coupling can be extended to several classes of polyhedral boranes including neutral and anionic carboranes, metallaboranes, and carbon-free boranes. Importantly, cross-coupling enables a suite of boron-heteroatom (C, N, O, P, S) couplings to prepare boron cluster-based systems that can be used for ligand design, medicinal chemistry, and materials applications.

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Li⁺‐Mediated BC Cross‐Coupling

Cited by 12 publications

References 41 publications

1,3‐Dehydro‐o‐Carborane: Generation and Reaction with Arenes

1,3‐Dehydro‐o‐Carborane: Generation and Reaction with Arenes

A Domino Approach to the Enantioselective Total Syntheses of Blennolide C and Gonytolide C

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

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Li+‐Mediated BC Cross‐Coupling

Cited by 12 publications

References 41 publications

1,3‐Dehydro‐o‐Carborane: Generation and Reaction with Arenes

1,3‐Dehydro‐o‐Carborane: Generation and Reaction with Arenes

A Domino Approach to the Enantioselective Total Syntheses of Blennolide C and Gonytolide C

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

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Li⁺‐Mediated BC Cross‐Coupling