Copper-catalyzed protoboration of borylated dendralenes: a regio- and stereoselective access to functionalized 1,3-dienes

Chaves-Pouso, Andrea; Rivera‐Chao, Eva; Fañanás‐Mastral, Martín

doi:10.1039/d0cc04018e

Cited by 14 publications

(7 citation statements)

References 34 publications

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“…We recently reported a catalytic methodology that allows the synthesis of borylated dendralenes from readily available alkynes, 1,4‐dibromo‐2‐butene and B 2 pin 2 [11] . As part of our studies on the functionalization of this new type of organoboronates, [11, 12] we attempted to transform 1 into methyl‐substituted dendralene 2 through a Zweifel coupling which would involve boronate complex formation, 1,2‐metallate rearrangement and deiodoborylation [13] . Surprisingly, when 1 was sequentially treated with 1 equiv of MeLi and iodine, no tractable amount of Zweifel coupling product 2 was detected.…”

Section: Methodsmentioning

confidence: 99%

Stereoselective Synthesis of Highly Substituted 1,3‐Dienes via “à la carte” Multifunctionalization of Borylated Dendralenes

Rivera‐Chao

Fañanás‐Mastral

2021

Angewandte Chemie

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Despite the high relevance of 1,3-dienes, stereoselective methods to access tetrasubstituted conjugated dienes are still scarce. We here report an efficient and modular approach that provides access to multifunctional tetrasubstituted 1,3dienes with excellent levels of regio-and stereoselectivity. This methodology is based on a tetracomponent reaction between a borylated dendralene, an organolithium reagent and two different electrophiles. Mechanistic studies reveal that this transformation proceeds through a regio-and stereoselective carbolithiation/electrophilic trapping of an in situ formed dendralenic boron-ate complex, followed by a stereoretentive halodeborylation. The ease in which complex structural dienes can be accessed and their synthetic versatility highlight the importance and utility of this method.Scheme 1. State-of-the-art methods for the stereoselective synthesis of highly substituted 1,3-dienes.

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Section: Methodsmentioning

confidence: 99%

Stereoselective Synthesis of Highly Substituted 1,3‐Dienes via “à la carte” Multifunctionalization of Borylated Dendralenes

Rivera‐Chao

Fañanás‐Mastral

2021

Angewandte Chemie

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“…表 2 铜催化的 1,2-二氢吡啶的不对称硼化质子化反应 [10] 报道了铜催化树枝烯的硼化质子化反应(表 5). 该方法在温和的反应条件下, 以较高的区域选择性生成 Z 构型的 1,4-加成产物.…”

Section: 铜催化共轭双烯的硼化质子化反应unclassified

“…基于控制实验观察和前人文献报道, 该课题组对树枝烯的硼化质子化反应机理进行了分析与推测(Scheme 4) [10] . 首先, 体系中生成的铜/硼配合物以 η 使用环状 α,β,γ,δ-不饱和酮衍生物作为原料时该反应也可以顺利进行 [12] .…”

Section: 铜催化共轭双烯的硼化质子化反应unclassified

Recent Advances about Protoboration of Conjugated Dienes

Zou¹,

Niu²,

Liu³

et al. 2021

Chinese Journal of Organic Chemistry

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The protoboration of conjugated diene is a kind of important strategy for the synthesis of allylic borides and homo-allylic borides, because of mild reaction conditions and wide functional group compatibility. Till now, several research groups have been reported key progress in this field, some of them could well control the chemical selectivity, regioselectivity and enantioselectivity of these transformations. In addition, some efficient tandem reactions which based on highly efficient protoboronation have been designed. These methods could be used for the synthesizing bioactive molecules via novel route. Furthermore, recently, the protoboronation of conjugated diene without transition metal catalyst has been realized. The research progress about protoboration of conjugated diene is summarized, the range of substrate scope is introduced, and the reaction mechanism for each reaction is discussed.

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“…Both hydroboration and diboration are well established for alkenes/alkynes 20 − 25 and also for more challenging allenes, 26 − 28 1,3-dienes, 29 − 32 and 1,3-enynes functionalization. 33 − 35 In contrast to this, the addition of boryl group(s) to 1,3-diynes is practically unexplored.…”

Section: Introductionmentioning

confidence: 99%

[Pt(PPh₃)₄]-Catalyzed Selective Diboration of Symmetrical and Unsymmetrical 1,3-Diynes

et al. 2022

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A straightforward, efficient, and selective method for the preparation of novel boryl-functionalized enynes or dienes via [Pt(PPh 3 ) 4 ]-catalyzed diboration of a broad spectrum of symmetrical and unsymmetrical 1,3-diynes was developed. The catalytic cycle of diboration was proposed on the basis of low-temperature 31 P NMR studies. An alternative isolation method via product condensation on a cold finger was developed, which, in contrast to previous literature reports, eliminates the need for the additional transformation of rapidly decomposing enynyl pinacol boronates to more stable silica-based column chromatography derivatives during the separation step. To prove the efficiency of this simple catalytic protocol, bisboryl-functionalized enynes were synthesized in a gram scale and tested as useful building blocks in advanced organic transformations, such as hydrosilylation and Suzuki and sila-Sonogashira couplings. The presence of silyl, boryl, as well as other functions like halogen or alkoxy in their structures builds a new class of multifunctionalized enynes that might be modified in various chemical reactions.

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Copper-catalyzed protoboration of borylated dendralenes: a regio- and stereoselective access to functionalized 1,3-dienes

Abstract: A copper-catalyzed protoboration of borylated dendralenes is reported. The method employs an NHC-Cu catalyst and provides access to 1,4-addition products with excellent levels of chemo-, regio- and stereoselectivity. The resulting...

Cited by 14 publications

References 34 publications

Stereoselective Synthesis of Highly Substituted 1,3‐Dienes via “à la carte” Multifunctionalization of Borylated Dendralenes

Stereoselective Synthesis of Highly Substituted 1,3‐Dienes via “à la carte” Multifunctionalization of Borylated Dendralenes

Recent Advances about Protoboration of Conjugated Dienes

[Pt(PPh₃)₄]-Catalyzed Selective Diboration of Symmetrical and Unsymmetrical 1,3-Diynes

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Copper-catalyzed protoboration of borylated dendralenes: a regio- and stereoselective access to functionalized 1,3-dienes

Abstract: A copper-catalyzed protoboration of borylated dendralenes is reported. The method employs an NHC-Cu catalyst and provides access to 1,4-addition products with excellent levels of chemo-, regio- and stereoselectivity. The resulting...

Cited by 14 publications

References 34 publications

Stereoselective Synthesis of Highly Substituted 1,3‐Dienes via “à la carte” Multifunctionalization of Borylated Dendralenes

Stereoselective Synthesis of Highly Substituted 1,3‐Dienes via “à la carte” Multifunctionalization of Borylated Dendralenes

Recent Advances about Protoboration of Conjugated Dienes

[Pt(PPh3)4]-Catalyzed Selective Diboration of Symmetrical and Unsymmetrical 1,3-Diynes

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[Pt(PPh₃)₄]-Catalyzed Selective Diboration of Symmetrical and Unsymmetrical 1,3-Diynes