Total Synthesis of (+)‐Asteriscanolide: Further Exploration of the Rhodium(I)‐Catalyzed [(5+2)+1] Reaction of Ene‐Vinylcyclopropanes and CO

Liang, Yong; Jiang, Xing; Xiao-yue, FU; Ye, Siyu; Wang, Tao; Yuan, Jie; Wang, Yuanyuan; Yu, Zhi‐Xiang

doi:10.1002/asia.201100805

Cited by 55 publications

(31 citation statements)

References 71 publications

(31 reference statements)

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“…Finally,t he use of TMP-AlMe 2 further increased steric hindrance and led to satisfactory yield and perfect regioselectivity (entry 3). [18] This crucial step,i nc ombination with the epoxidation reaction, efficiently created the desired hydroxymethyl moiety and enabled the final ring closure.…”

Section: Methodsmentioning

confidence: 99%

Total Synthesis of (+)‐Minfiensine: Construction of the Tetracyclic Core Structure by an Asymmetric Cascade Cyclization

2016

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A new method for one-step construction of the tetracyclic core structure of the indole alkaloid (+)-minfiensine was developed utilizing a palladium-catalyzed asymmetric indole dearomatization/iminium cyclization cascade. An efficient total synthesis of (+)-minfiensine was realized using this strategy. The present method enables access to the common core structure of a series of monoterpene indole alkaloids, such as vincorine, echitamine, and aspidosphylline A.

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Section: Methodsmentioning

confidence: 99%

Total Synthesis of (+)‐Minfiensine: Construction of the Tetracyclic Core Structure by an Asymmetric Cascade Cyclization

2016

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“…57 Another example for the application of [5 + 2 + 1] cycloaddition is the total synthesis of (+)-asteriscanolide, 30 (Scheme 9). 54,60 There are two key reactions in our synthetic route. One is the rhodium-catalyzed [5 + 2 + 1] cycloaddition of a chiral ene−VCP substrate 26 and CO, which efficiently constructs the bicyclo[6.3.0]undecane skeleton with excellent asymmetric induction and diastereoselectivity.…”

Section: ■ Synthetic Applicationsmentioning

confidence: 99%

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

Wang

2015

Acc. Chem. Res.

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188

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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 cycloadditions 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-vinylcyclopropanes (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 + 1] 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 + 1] 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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“…[1] Transition-metal-catalyzed [m+n] and/or [m+n+o] cycloadditions (e.g., [4+4], [6+2], and [4+2+2]) are the most promising strategies for the construction of polycyclic eight-membered-ring compounds. [2,3] However, the construction of a simple but functionalized monocyclic eightmembered carbocyclic system is still difficult even when using transition-metal-catalyzed cycloadditions, and only a few examples have so far been reported. [4] Herein we report Rh I -catalyzed intermolecular [6+2] cycloadditions of 4-allenals and alkynes to give functionalized monocyclic eightmembered-ring compounds.…”

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confidence: 99%

Construction of Monocyclic Eight‐Membered Rings: Intermolecular Rhodium(I)‐Catalyzed [6+2] Cycloaddition of 4‐Allenals with Alkynes

2012

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Eight-membered carbocyclic compounds are widely found in natural products that have unique medical and biological activities. [1] Transition-metal-catalyzed [m+n] and/or [m+n+o] cycloadditions (e.g., [4+4], [6+2], and [4+2+2]) are the most promising strategies for the construction of polycyclic eight-membered-ring compounds. [2,3] However, the construction of a simple but functionalized monocyclic eightmembered carbocyclic system is still difficult even when using transition-metal-catalyzed cycloadditions, and only a few examples have so far been reported. [4] Herein we report Rh I -catalyzed intermolecular [6+2] cycloadditions of 4-allenals and alkynes to give functionalized monocyclic eightmembered-ring compounds. [4f, 5-8] We recently reported a Rh I -catalyzed intramolecular [6+2] cycloaddition of 4-allenals with tethered alkynes and alkenes (Scheme 1). [5c] In this reaction, the rhodacycle A is initially formed through hydroacylation [9] of the 4-allenal moiety of 1 followed by insertion into a C À C mutiple bond in the tether to afford bicyclic eight-membered-ring compound 2.We envisaged that if this intramolecular [6+2] cycloaddition could be expanded to an intermolecular reaction between 4-allenal 3 and alkyne 4, monocyclic octanone derivative 5 would be obtained (Scheme 2). [10] However, the application of the intramolecular reaction to an intermolecular version is generally difficult because of unfavorable entropy and the high probability of side reactions (e.g., formation of 6 through hydroacylation of allenal 3 [5c] and formation of 7 by trimerization of alkyne 4).To examine the feasibility of the plan, the cyclization of 4allenal 3 a with terminal alkyne 4 a in the presence of various Rh I complexes was initially investigated (Table 1). The use of [Rh(IMes)(cod)]ClO 4 , which is the most effective for the above-mentioned intramolecular cyclization (Scheme 1), afforded the desired eight-membered ring 5 aa in 61 % yield along with six-membered ring 8 aa in 19 % yield (entry 1). [11] It was found that [Rh(SIMes)(cod)]ClO 4 was also effective in this intermolecular reaction, and the cyclic compound 5 aa was produced selectively in 68 % yield (entry 2). Lowering the reaction temperature from room temperature to 0 8C improved the yield of the eight-membered-ring compound 5 aa up to 83 % (entry 3). Furthermore, the catalyst loading could be reduced to 2 mol % under similar reaction conditions, thereby giving 5 aa in 84 % yield (entry 4). On the other hand, [RhCl(PPh 3 ) 3 ] and [Rh(dppe)]ClO 4 did not promote the desired reaction at all, and the starting material 3 a was recovered in 69 % and 78 % yield, respectively (entries 5 and 6).Encouraged by these results, the cyclization of 4-allenal 3 a with various terminal alkynes 4 was examined ( Table 2). Cyclization of 3 a with terminal alkynes 4 b, 4 c, and 4 d, having Scheme 1. Rh I -catalyzed intramolecular [6+2] cycloaddition. L = ligand. Scheme 2. Plan for intermolecular [6+2] cycloaddition.

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Total Synthesis of (+)‐Asteriscanolide: Further Exploration of the Rhodium(I)‐Catalyzed [(5+2)+1] Reaction of Ene‐Vinylcyclopropanes and CO

Cited by 55 publications

References 71 publications

Total Synthesis of (+)‐Minfiensine: Construction of the Tetracyclic Core Structure by an Asymmetric Cascade Cyclization

Total Synthesis of (+)‐Minfiensine: Construction of the Tetracyclic Core Structure by an Asymmetric Cascade Cyclization

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

Construction of Monocyclic Eight‐Membered Rings: Intermolecular Rhodium(I)‐Catalyzed [6+2] Cycloaddition of 4‐Allenals with Alkynes

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