Total Synthesis of (+)-Irciniastatin A (a.k.a. Psymberin) and (−)-Irciniastatin B

An, Chihui; Jurica, Jon A.; Walsh, Shawn P.; Hoye, Adam T.; Smith, Amos B.

doi:10.1021/jo400260m

Cited by 33 publications

(21 citation statements)

References 48 publications

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“…[7c] Common inter-Scheme 18. Synthesis of irciniastatin A (psymberin) and irciniastatin B (Smith, 2008(Smith, , 2013. [49] Ipc = isopinocampheyl, SEM = 2-trimethylsilylethoxymethoxy.…”

Section: Control By Chiral Auxiliaries and Reagentsmentioning

confidence: 99%

The Impact of the Mukaiyama Aldol Reaction in Total Synthesis

2013

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Four decades since Mukaiyama's first reports on the successful application of silicon and boron enolates in directed aldol reactions, the ability of this highly controlled carbon-carbon bond-forming method to simultaneously define stereochemistry, introduce complexity, and construct the carbon skeleton with a characteristic 1,3-oxygenation pattern has made it a powerful tool for natural product synthesis. This Minireview highlights a number of representative total syntheses that demonstrate the impact of the Mukaiyama aldol reaction and discusses the underlying mechanistic rationale that determines the stereochemical outcomes.

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“…[7c] Common inter-Scheme 18. Synthesis of irciniastatin A (psymberin) and irciniastatin B (Smith, 2008(Smith, , 2013. [49] Ipc = isopinocampheyl, SEM = 2-trimethylsilylethoxymethoxy.…”

Section: Control By Chiral Auxiliaries and Reagentsmentioning

confidence: 99%

The Impact of the Mukaiyama Aldol Reaction in Total Synthesis

2013

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“…We began the synthesis of acid (−)- 12 by protection of alcohol (+)- 17 , 19 prepared previously in our synthesis of irciniastatins as the TBS ether, followed by reductive removal of the pivalate group to furnish (+)- 18 ( Scheme 2 ). A two-step oxidation sequence yielded the desired acid (−)- 12 in 70% yield for the two steps.…”

Section: Resultsmentioning

confidence: 99%

Design, Synthesis, and Evaluation of Irciniastatin Analogues: Simplification of the Tetrahydropyran Core and the C(11) Substituents

Liu

Tendyke

et al. 2016

J. Org. Chem.

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The design, synthesis, and biological evaluation of irciniastatin A (1) analogues, achieved by removal of three synthetically challenging structural units, as well as by functional group manipulation of the C(11) substituent of both irciniastatins A and B (1 and 2), has been achieved. To this end, we first designed a convergent synthetic route toward the diminutive analogue (+)-C(8)-desmethoxy-C(11)-deoxy-C(12)-didesmethylirciniastatin (6). Key transformations include an acid-catalyzed 6-exo-tet pyran cyclization, a chiral Lewis acid mediated aldol reaction, and a facile amide union. The absolute configuration of 6 was confirmed via spectroscopic analysis (CD spectrum, HSQC, COSY, and ROESY NMR experiments). Structure–activity relationship (SAR) studies of 6 demonstrate that the absence of the three native structural units permits access to analogues possessing cytotoxic activity in the nanomolar range. Second, manipulation of the C(11) position, employing late-stage synthetic intermediates from our irciniastatin syntheses, provides an additional five analogues (7–11). Biological evaluation of these analogues indicates a high functional group tolerance at position C(11).

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“…[ 16 ] In Smith's synthesis of (+)‐irciniastatin A ( 59 ), epoxide 57 was prepared via asymmetric epoxidation of conjugated diene ester 56 , followed by an AlMe 3 mediated epoxide‐opening reaction to give 58 (Scheme 15). [ 46 ]…”

Section: The Application Of Shi Epoxidationmentioning

confidence: 99%

Shi Epoxidation: A Great Shortcut to Complex Compounds

Feng

2021

Chin. J. Chem.

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Shi epoxidation provides an extremely powerful tool to access optically active epoxides, which undoubtedly belongs to one of the earliest and most successful organocatalytic systems. Several generations of chiral ketones have been developed to realize the asymmetric epoxidation of each type of unfunctionalized alkenes, including trans‐, trisubstituted olefins, cis‐olefins, terminal olefins, and tetrasubstituted olefins. Due to its reliability and high regio‐ and enantioselectivity, Shi epoxidation has been widely applied in the synthesis of complex natural products and biologically active molecules.

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Total Synthesis of (+)-Irciniastatin A (a.k.a. Psymberin) and (−)-Irciniastatin B

Cited by 33 publications

References 48 publications

The Impact of the Mukaiyama Aldol Reaction in Total Synthesis

The Impact of the Mukaiyama Aldol Reaction in Total Synthesis

Design, Synthesis, and Evaluation of Irciniastatin Analogues: Simplification of the Tetrahydropyran Core and the C(11) Substituents

Shi Epoxidation: A Great Shortcut to Complex Compounds

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