Total Syntheses of Cyanthiwigins B, F, and G

Enquist, John A.; Virgil, Scott C.; Stoltz, Brian M.

doi:10.1002/chem.201100425

Cited by 47 publications

(27 citation statements)

References 72 publications

(37 reference statements)

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“…Syntheses of other members of the cyanthiwigin natural product family utilised the same powerful 'stereoablative' method. [173] The advanced synthetic technology on show in this reaction illustrates the level to which two-directional methods have evolved over the past three decades. This synthesis also features a pair of independent metathesis reactions carried out in a one-pot manner (Scheme 27b): one a ring-closing and the other a cross-metathesis process.…”

Section: Independent Reactionsmentioning

confidence: 97%

Multi-Bond Forming Processes in Efficient Synthesis

Green¹,

Sherburn²

2013

Aust. J. Chem.

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An increasing number of synthetic organic chemists are embracing the philosophy of efficiency. Herein we highlight multi-bond forming processes, which form two or more new covalent bonds in a single synthetic operation. Such processes, which have the ability to rapidly increase structural complexity, are preeminent in contemporary synthetic organic chemistry. In this short review we classify, analyse, and contrast contemporary multi-bond forming processes, frame these cutting edge contributions within a historical context, and speculate on likely future developments in the area.

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Section: Independent Reactionsmentioning

confidence: 97%

Multi-Bond Forming Processes in Efficient Synthesis

Green¹,

Sherburn²

2013

Aust. J. Chem.

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“…These efforts culminated in efficient total syntheses of cyanthiwigins B, F, and G ( 124 , 126 , and 127 , Scheme 17, below). [43] …”

Section: Catalytic Asymmetric Synthesis Of Natural Productsmentioning

confidence: 99%

“…Studies on the related bis-β-keto ester double alkylation substrate 117 provided product 118 in 78% yield, 99% ee , and 4.4:1 dr . [43] These impressive levels of asymmetric induction can be explained by statistical amplification resulting from multiple asymmetric transformations occurring in sequence. [44,45] The efficiency of these transformations for the assembly of two all-carbon quaternary stereocenters in the same ring system provided an excellent foundation for further synthetic efforts directed towards the cyathane diterpenoids.…”

Section: Catalytic Asymmetric Synthesis Of Natural Productsmentioning

confidence: 99%

The Construction of All‐Carbon Quaternary Stereocenters by Use of Pd‐Catalyzed Asymmetric Allylic Alkylation Reactions in Total Synthesis

2013

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All-carbon quaternary stereocenters have posed significant challenges in the synthesis of complex natural products. These important structural motifs have inspired the development of broadly applicable palladium-catalyzed asymmetric allylic alkylation reactions of unstabilized non-biased enolates for the synthesis of enantioenriched α-quaternary products. This microreview outlines key considerations in the application of palladium-catalyzed asymmetric allylic alkylation reactions and presents recent total syntheses of complex natural products that have employed these powerful transformations for the direct, catalytic, enantioselective construction of all-carbon quaternary stereocenters.

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“…Recently, an excellent application of a Negishi cross-coupling with a homoallylzinc reagent and alkenyl triflate was reported for the total synthesis of cyanthiwigins B, F, and G (Scheme 3.58) [228]. Stoltz et al overcame difficulties generated by other cross-coupling reactions and chose Negishi coupling to generate the 6,7-membered fused-ring backbone followed by ring-closing metathesis employing a Grubb's catalyst to avoid the intramolecular Heck reaction by-product which is inseparable (Eq.…”

Section: Bibenzyls Homoallylarenes 15-dienes Homopropargylarenesmentioning

confidence: 99%

Pd‐Catalyzed Cross‐Coupling with Organometals Containing Zn, Al, Zr, and so on – The Negishi Coupling and Its Recent Advances

Kamada

Kim

et al. 2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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The Pd-or Ni-catalyzed cross-coupling reactions of organometals containing Zn, Al, Zr, and B as well as related reactions of those containing Mg and several other metals collectively have emerged as arguably the most widely applicable organic skeleton construction method discovered and developed over the past several decades, allowing synthetic chemists to prepare practically all types of organic compounds. In this chapter, some of the seminal and critically important discoveries and early developments in the 1970s as well as their current scope are briefly discussed. Some of the notable discoveries and developments include (i) identification of superior properties of Pd as a critical element for crosscoupling relative to Ni, (ii) the broad scope of Pd-or Ni-catalyzed cross-coupling with respect to metal countercations including Zn, Al, Zr, B, and Mg, (iii) the hydrometallation-Pd-catalyzed cross-coupling sequential processes for selective syntheses of alkenes, dienes, oligoenes, and oligoenynes, (iv) double metal catalysis involving Pd or Ni and added metal compounds containing Zn, In, Li, and others, and (v) realization of high turnover numbers (TONs) (≥10 3 -10 9 ) through the use of chelating phosphines, such as bis-[2-(diphenylphosphino)phenyl] ether (DPEphos) and 1,1 -Bis(diphenylphosphino)ferrocene (dppf).The Zr-catalyzed alkyne carboalumination and the Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction) have provided efficient and selective routes to (E)-trisubstituted alkenylalanes and 2-substituted chiral alkylalanes, respectively. These reactions provide two additional examples of prototypical transition metal-catalyzed organometallic reactions. Significantly, they can be readily combined with the Pd-or Ni-catalyzed cross-coupling for the synthesis of trisubstituted alkenes embracing a wide variety of natural products, such as terpenoids, carotenoids, and others, as well as various chiral organics including deoxypolypropionates and saturated terpenoids. The Zr-catalyzed alkyne carboalumination has been applied to the synthesis of a large number (>100) of natural products, while the ZACA reaction has been transformed from a mere scientific novelty to a full-fledged asymmetric synthetic method that is catalytic in both transition metal (Zr) and chiral auxiliaries through a series of breakthroughs.

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Total Syntheses of Cyanthiwigins B, F, and G

Cited by 47 publications

References 72 publications

Multi-Bond Forming Processes in Efficient Synthesis

Multi-Bond Forming Processes in Efficient Synthesis

The Construction of All‐Carbon Quaternary Stereocenters by Use of Pd‐Catalyzed Asymmetric Allylic Alkylation Reactions in Total Synthesis

Pd‐Catalyzed Cross‐Coupling with Organometals Containing Zn, Al, Zr, and so on – The Negishi Coupling and Its Recent Advances

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