Rhodium(<scp>I</scp>)‐Catalyzed Reactions<scp>via</scp>Carbon–Hydrogen Bond Cleavage

Shibata, Takanori

doi:10.1002/9783527811908.ch11

Cited by 7 publications

(5 citation statements)

References 62 publications

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“…However, under different optimized conditions, 11 or 12 was obtained in 33% or 67% yield, respectively. The formation of 11 indicated the expected carbonylative annulation reaction had indeed proceeded and provided the desired C13 quaternary center, but the resultant product underwent a further Rh-catalyzed carbonylative C–H insertion to afford 11 . While the formation of 12 could be a result of a double bond isomerization followed by a PK reaction.…”

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confidence: 99%

Asymmetric Total Synthesis of (−)-Spirochensilide A

2020

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An asymmetric total synthesis of (−)-spirochensilide A has been achieved for the first time. The synthesis features a semipinacol rearrangement reaction to stereoselectively construct the two-vicinal quaternary chiral centers at C8 and C10, a tungsten-mediated cyclopropene-based Pauson–Khand reaction to install the C13 quaternary chiral center, and a furan-based oxidative cyclization to stereoselectively form the spiroketal motif.

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confidence: 99%

Asymmetric Total Synthesis of (−)-Spirochensilide A

2020

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“…To make our total synthesis more concise, we intended to form the C–C bond between C17 and C21 in intermediate A through an intermolecular aldol condensation under Mukaiyama condition between cyclopentanone B and furyl acetaldehyde C . To install the pivotal C13 methyl group of the CD ring in B , we wished to employ emerging methods, such as a tungsten-mediated cyclopropene-based Pauson–Khand (PK) reaction, to form cyclopropane-fused cyclopentenone D , which might afford the C13 methyl group after a regioselective and reductive cyclopropane ring opening. Therefore, our retrosynthetic analysis was traced back to the stereoselective formation of enyne E , which could be obtained from the alkylation of aldehyde F using chemistry developed in our previous paper.…”

Section: Results and Discussionmentioning

confidence: 99%

Asymmetric Total Synthesis of (−)-Spirochensilide A, Part 2: The Final Phase and Completion

et al. 2021

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The final phase of the total synthesis of (−)-spirochensilide A is described. A tungsten-mediated cyclopropene-based Pauson−Khand reaction was developed to form the spiral CD ring system with desired stereochemistry at the C13 quaternary center. Other important steps enabling completion of this synthesis included an intermolecular aldol condensation to link the ABCD core with the EF fragment and a Cu-mediated 1,4-addition to stereoselectively install the C21 stereogenic center. The chemistry developed for this total synthesis of (−)-spirochensilide A (1) will aid the synthesis of polycyclic natural products bearing this unique spiral ring system.

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“…As the energy supplied at 65 °C seemed insufficient to construct a quaternary center in the (sub-) rate-determining step of the PK reaction, chloroenyne 41 was reacted with [Rh(CO) 2 Cl] 2 in n Bu 2 O under a CO atmosphere at a higher temperature of 160 °C, affording 43 in 33% yield. Formation of 43 indicated that the expected PK reaction had proceeded, providing the desired C13 quaternary center, but the resultant product underwent a further Rh-catalyzed cross-coupling reaction through intermediates 43a and 43b to afford polycyclic product 43 . To the best of our knowledge, this is the first Rh-mediated sp 2 C–Cl/sp 3 C–H coupling reaction.…”

Section: Resultsmentioning

confidence: 99%

Asymmetric Total Synthesis of (−)-Spirochensilide A, Part 1: Diastereoselective Synthesis of the ABCD Ring and Stereoselective Total Synthesis of 13(R)-Demethyl Spirochensilide A

et al. 2021

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A concise and diastereoselective construction of the ABCD ring system of spirochensilide A is described. The key steps of this synthesis are a semipinacol rearrangement reaction to stereoselectively construct the AB ring system bearing two vicinal quaternary chiral centers and a Co-mediated Pauson−Khand reaction to form the spiro-based bicyclic CD ring system. This chemistry leads to the stereoselective synthesis of 13(R)-demethyl spirochensilide A, paving the way for the first asymmetric total synthesis of (−)-spirochensilide A.

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Rhodium(I)‐Catalyzed ReactionsviaCarbon–Hydrogen Bond Cleavage

Cited by 7 publications

References 62 publications

Asymmetric Total Synthesis of (−)-Spirochensilide A

Asymmetric Total Synthesis of (−)-Spirochensilide A

Asymmetric Total Synthesis of (−)-Spirochensilide A, Part 2: The Final Phase and Completion

Asymmetric Total Synthesis of (−)-Spirochensilide A, Part 1: Diastereoselective Synthesis of the ABCD Ring and Stereoselective Total Synthesis of 13(R)-Demethyl Spirochensilide A

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