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Yi Wang - One of the best experts on this subject based on the ideXlab platform.
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rhodium catalyzed 5 2 1 cycloaddition of ene vinylcyclopropanes and co reaction design development application in natural Product Synthesis and inspiration for developing new reactions for Synthesis of eight membered carbocycles
Accounts of Chemical Research, 2015Co-Authors: Yi Wang, Zhi-xiang YuAbstract:CONSPECTUS: Practical syntheses of natural Products and their analogues with eight-membered carbocyclic skeletons are important for medicinal and biological investigations. However, methods and strategies to construct the eight-membered carbocycles are limited. Therefore, developing new methods to synthesize the eight-membered carbocycles is highly desired. In this Account, we describe our development of three rhodium-catalyzed cyclo-additions for the construction of the eight-membered carbocycles, which have great potential in addressing the challenges in the Synthesis of medium-sized ring systems. The first reaction described in this Account is our computationally designed rhodium-catalyzed two-component [5 + 2 + 1] cycloaddition of ene-vinylcydopropanes (ene-VCPs) and CO for the diastereoselective construction of bi- and tricyclic cyclooctenones. The design of this reaction is based on the hypothesis that the C(sp(3))-C(sp(3)) reductive elimination of the eight-membered rhodacycle intermediate generated from the rhodium-catalyzed cyclopropane cleavage and alkene insertion, giving Wender's [5 + 2] cycloadduct, is not easy. Under CO atmosphere, CO insertion may occur rapidly, converting the eight-membered rhodacycle into a nine-membered rhodacycle, which then undergoes an easy C(sp(2))-C(sp(3)) reductive elimination process and furnishes the [5 + 2 + 1] Product. This hypothesis was supported by our preliminary DFT studies and also served as inspiration for the development of two [7 + I] cycloadditions: the [7 + 1] cycloaddition of buta-1,3-dienylcyclopropanes (BDCPs) and CO for the construction of cyclooctadienones, and the benzo/[7 + 1] cycloaddition of cyclopropyl-benzocyclobutenes (CP-BCBs) and CO to synthesize the benzocyclooctenones. The efficiency of these rhodium-catalyzed cycloadditions can be revealed by the application in natural Product Synthesis. Two eight-membered ring-containing natural Products, (+/-)-asterisca-3(15),6-diene and (+)-asteriscanolide, have been synthesized using the [5 + 2 + 1] cycloaddition as the key step. In the latter case, excellent asymmetric induction was obtained using a chiral substrate. The efficiency of the [5 + 2 + 1] reaction was further demonstrated by the Synthesis of four sesquiterpene natural Products, (+/-)-pentalenene, (+)-hirsutene, (+/-)-1-desoxyhypnophilin, and (+/-)-hirsutic acid C, containing linear or branched triquinane skeletons utilizing the tandem or stepwise [5 + 2 + 1] cycloaddition/aldol reaction strategy. With the success of [5 + 2 + I] cycloaddition in natural Product Synthesis, application of the [7 + 1] and benzo/[7 + 1] cycloadditions in target- and function-oriented syntheses can be envisioned.
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Rhodium-Catalyzed [5+2+1] Cycloaddition of Ene-Vinylcyclopropanes and CO: Reaction Design, Development, Application in Natural Product Synthesis, and Inspiration for Developing New Reactions for Synthesis of Eight-Membered Carbocycles
ACCOUNTS OF CHEMICAL RESEARCH, 2015Co-Authors: Yi Wang, Yu Zhi-xiangAbstract:CONSPECTUS: Practical syntheses of natural Products and their analogues with eight-membered carbocyclic skeletons are important for medicinal and biological investigations. However, methods and strategies to construct the eight-membered carbocycles are limited. Therefore, developing new methods to synthesize the eight-membered carbocycles is highly desired. In this Account, we describe our development of three rhodium-catalyzed cyclo-additions for the construction of the eight-membered carbocycles, which have great potential in addressing the challenges in the Synthesis of medium-sized ring systems. The first reaction described in this Account is our computationally designed rhodium-catalyzed two-component [5 + 2 + 1] cycloaddition of ene-vinylcydopropanes (ene-VCPs) and CO for the diastereoselective construction of bi- and tricyclic cyclooctenones. The design of this reaction is based on the hypothesis that the C(sp(3))-C(sp(3)) reductive elimination of the eight-membered rhodacycle intermediate generated from the rhodium-catalyzed cyclopropane cleavage and alkene insertion, giving Wender's [5 + 2] cycloadduct, is not easy. Under CO atmosphere, CO insertion may occur rapidly, converting the eight-membered rhodacycle into a nine-membered rhodacycle, which then undergoes an easy C(sp(2))-C(sp(3)) reductive elimination process and furnishes the [5 + 2 + 1] Product. This hypothesis was supported by our preliminary DFT studies and also served as inspiration for the development of two [7 + I] cycloadditions: the [7 + 1] cycloaddition of buta-1,3-dienylcyclopropanes (BDCPs) and CO for the construction of cyclooctadienones, and the benzo/[7 + 1] cycloaddition of cyclopropyl-benzocyclobutenes (CP-BCBs) and CO to synthesize the benzocyclooctenones. The efficiency of these rhodium-catalyzed cycloadditions can be revealed by the application in natural Product Synthesis. Two eight-membered ring-containing natural Products, (+/-)-asterisca-3(15),6-diene and (+)-asteriscanolide, have been synthesized using the [5 + 2 + 1] cycloaddition as the key step. In the latter case, excellent asymmetric induction was obtained using a chiral substrate. The efficiency of the [5 + 2 + 1] reaction was further demonstrated by the Synthesis of four sesquiterpene natural Products, (+/-)-pentalenene, (+)-hirsutene, (+/-)-1-desoxyhypnophilin, and (+/-)-hirsutic acid C, containing linear or branched triquinane skeletons utilizing the tandem or stepwise [5 + 2 + 1] cycloaddition/aldol reaction strategy. With the success of [5 + 2 + I] cycloaddition in natural Product Synthesis, application of the [7 + 1] and benzo/[7 + 1] cycloadditions in target- and function-oriented syntheses can be envisioned.Natural Science Foundation of China [20672005, 21232001]; National Basic Research Program of China-973 Program [2011CB808600]SCI(E)PubMedREVIEWyuzx@pku.edu.cn82288-22964
Mark R J Elsegood - One of the best experts on this subject based on the ideXlab platform.
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a highly stereoselective Synthesis of the indolo 2 3 a quinolizine ring system and application to natural Product Synthesis
European Journal of Organic Chemistry, 2005Co-Authors: Steven M. Allin, Christopher I Thomas, Kevin J Doyle, James E Allard, Mark R J ElsegoodAbstract:We present a facile and highly stereoselective approach to the indolo[2,3-a]quinolizine ring system from a readily available, non-racemic chiral template. We demonstrate the potential for application of this methodology to natural Product Synthesis through conversion of the template to some representative indole alkaloids with high enantiomeric purity in both enantiomeric series. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
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highly stereoselective Synthesis of the indolo 2 3 a quinolizine ring system and application to indole natural Product Synthesis
Tetrahedron Letters, 2004Co-Authors: Steven M. Allin, Christopher I Thomas, Kevin J Doyle, James E Allard, Mark R J ElsegoodAbstract:We report a novel, facile and highly stereoselective approach to the indolo[2,3-a]quinolizine ring system from a readily available, non-racemic chiral template. We demonstrate the potential for application of this methodology to natural Product Synthesis through conversion of the template to a simple indole alkaloid with high enantiomeric purity.
Zhi-xiang Yu - One of the best experts on this subject based on the ideXlab platform.
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rhodium catalyzed 5 2 1 cycloaddition of ene vinylcyclopropanes and co reaction design development application in natural Product Synthesis and inspiration for developing new reactions for Synthesis of eight membered carbocycles
Accounts of Chemical Research, 2015Co-Authors: Yi Wang, Zhi-xiang YuAbstract:CONSPECTUS: Practical syntheses of natural Products and their analogues with eight-membered carbocyclic skeletons are important for medicinal and biological investigations. However, methods and strategies to construct the eight-membered carbocycles are limited. Therefore, developing new methods to synthesize the eight-membered carbocycles is highly desired. In this Account, we describe our development of three rhodium-catalyzed cyclo-additions for the construction of the eight-membered carbocycles, which have great potential in addressing the challenges in the Synthesis of medium-sized ring systems. The first reaction described in this Account is our computationally designed rhodium-catalyzed two-component [5 + 2 + 1] cycloaddition of ene-vinylcydopropanes (ene-VCPs) and CO for the diastereoselective construction of bi- and tricyclic cyclooctenones. The design of this reaction is based on the hypothesis that the C(sp(3))-C(sp(3)) reductive elimination of the eight-membered rhodacycle intermediate generated from the rhodium-catalyzed cyclopropane cleavage and alkene insertion, giving Wender's [5 + 2] cycloadduct, is not easy. Under CO atmosphere, CO insertion may occur rapidly, converting the eight-membered rhodacycle into a nine-membered rhodacycle, which then undergoes an easy C(sp(2))-C(sp(3)) reductive elimination process and furnishes the [5 + 2 + 1] Product. This hypothesis was supported by our preliminary DFT studies and also served as inspiration for the development of two [7 + I] cycloadditions: the [7 + 1] cycloaddition of buta-1,3-dienylcyclopropanes (BDCPs) and CO for the construction of cyclooctadienones, and the benzo/[7 + 1] cycloaddition of cyclopropyl-benzocyclobutenes (CP-BCBs) and CO to synthesize the benzocyclooctenones. The efficiency of these rhodium-catalyzed cycloadditions can be revealed by the application in natural Product Synthesis. Two eight-membered ring-containing natural Products, (+/-)-asterisca-3(15),6-diene and (+)-asteriscanolide, have been synthesized using the [5 + 2 + 1] cycloaddition as the key step. In the latter case, excellent asymmetric induction was obtained using a chiral substrate. The efficiency of the [5 + 2 + 1] reaction was further demonstrated by the Synthesis of four sesquiterpene natural Products, (+/-)-pentalenene, (+)-hirsutene, (+/-)-1-desoxyhypnophilin, and (+/-)-hirsutic acid C, containing linear or branched triquinane skeletons utilizing the tandem or stepwise [5 + 2 + 1] cycloaddition/aldol reaction strategy. With the success of [5 + 2 + I] cycloaddition in natural Product Synthesis, application of the [7 + 1] and benzo/[7 + 1] cycloadditions in target- and function-oriented syntheses can be envisioned.
Yu Zhi-xiang - One of the best experts on this subject based on the ideXlab platform.
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Rhodium-Catalyzed [5+2+1] Cycloaddition of Ene-Vinylcyclopropanes and CO: Reaction Design, Development, Application in Natural Product Synthesis, and Inspiration for Developing New Reactions for Synthesis of Eight-Membered Carbocycles
ACCOUNTS OF CHEMICAL RESEARCH, 2015Co-Authors: Yi Wang, Yu Zhi-xiangAbstract:CONSPECTUS: Practical syntheses of natural Products and their analogues with eight-membered carbocyclic skeletons are important for medicinal and biological investigations. However, methods and strategies to construct the eight-membered carbocycles are limited. Therefore, developing new methods to synthesize the eight-membered carbocycles is highly desired. In this Account, we describe our development of three rhodium-catalyzed cyclo-additions for the construction of the eight-membered carbocycles, which have great potential in addressing the challenges in the Synthesis of medium-sized ring systems. The first reaction described in this Account is our computationally designed rhodium-catalyzed two-component [5 + 2 + 1] cycloaddition of ene-vinylcydopropanes (ene-VCPs) and CO for the diastereoselective construction of bi- and tricyclic cyclooctenones. The design of this reaction is based on the hypothesis that the C(sp(3))-C(sp(3)) reductive elimination of the eight-membered rhodacycle intermediate generated from the rhodium-catalyzed cyclopropane cleavage and alkene insertion, giving Wender's [5 + 2] cycloadduct, is not easy. Under CO atmosphere, CO insertion may occur rapidly, converting the eight-membered rhodacycle into a nine-membered rhodacycle, which then undergoes an easy C(sp(2))-C(sp(3)) reductive elimination process and furnishes the [5 + 2 + 1] Product. This hypothesis was supported by our preliminary DFT studies and also served as inspiration for the development of two [7 + I] cycloadditions: the [7 + 1] cycloaddition of buta-1,3-dienylcyclopropanes (BDCPs) and CO for the construction of cyclooctadienones, and the benzo/[7 + 1] cycloaddition of cyclopropyl-benzocyclobutenes (CP-BCBs) and CO to synthesize the benzocyclooctenones. The efficiency of these rhodium-catalyzed cycloadditions can be revealed by the application in natural Product Synthesis. Two eight-membered ring-containing natural Products, (+/-)-asterisca-3(15),6-diene and (+)-asteriscanolide, have been synthesized using the [5 + 2 + 1] cycloaddition as the key step. In the latter case, excellent asymmetric induction was obtained using a chiral substrate. The efficiency of the [5 + 2 + 1] reaction was further demonstrated by the Synthesis of four sesquiterpene natural Products, (+/-)-pentalenene, (+)-hirsutene, (+/-)-1-desoxyhypnophilin, and (+/-)-hirsutic acid C, containing linear or branched triquinane skeletons utilizing the tandem or stepwise [5 + 2 + 1] cycloaddition/aldol reaction strategy. With the success of [5 + 2 + I] cycloaddition in natural Product Synthesis, application of the [7 + 1] and benzo/[7 + 1] cycloadditions in target- and function-oriented syntheses can be envisioned.Natural Science Foundation of China [20672005, 21232001]; National Basic Research Program of China-973 Program [2011CB808600]SCI(E)PubMedREVIEWyuzx@pku.edu.cn82288-22964
Steven M. Allin - One of the best experts on this subject based on the ideXlab platform.
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a highly stereoselective Synthesis of the indolo 2 3 a quinolizine ring system and application to natural Product Synthesis
European Journal of Organic Chemistry, 2005Co-Authors: Steven M. Allin, Christopher I Thomas, Kevin J Doyle, James E Allard, Mark R J ElsegoodAbstract:We present a facile and highly stereoselective approach to the indolo[2,3-a]quinolizine ring system from a readily available, non-racemic chiral template. We demonstrate the potential for application of this methodology to natural Product Synthesis through conversion of the template to some representative indole alkaloids with high enantiomeric purity in both enantiomeric series. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
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highly stereoselective Synthesis of the indolo 2 3 a quinolizine ring system and application to indole natural Product Synthesis
Tetrahedron Letters, 2004Co-Authors: Steven M. Allin, Christopher I Thomas, Kevin J Doyle, James E Allard, Mark R J ElsegoodAbstract:We report a novel, facile and highly stereoselective approach to the indolo[2,3-a]quinolizine ring system from a readily available, non-racemic chiral template. We demonstrate the potential for application of this methodology to natural Product Synthesis through conversion of the template to a simple indole alkaloid with high enantiomeric purity.
