Triphenylphosphine Dichloride

Dormoy, Jean‐Robert; Castro, Bertrand

doi:10.1002/047084289x.rt371

Cited by 2 publications

(2 citation statements)

References 36 publications

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“…Our preliminary experiments which were carried out with traditional chlorinating reagents such as PCl 5 , proved to be problematic and afforded a mixture of products . We also explored the chlorination of (+)‐ 10 with dichlorotriphenylphosphorane (Ph 3 PCl 2 ) as an alternative to the previous method , . The reaction was carried out in the presence of TMEDA as the base and afforded oxazolidinone (–)‐ 11 as the sole product.…”

Section: Resultsmentioning

confidence: 99%

Formal Synthesis of (–)‐Perhydrohistrionicotoxin Using a Thorpe‐Ziegler Cyclization Approach. Synthesis of Functionalized Aza‐Spirocycles

Bouvry

Roisnel

et al. 2018

Eur J Org Chem

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The formal synthesis of (–)‐PHTX is described. Our approach was based on the anodic cyanation of (S)‐1‐(1‐phenylethyl)‐piperidine (–)‐1 to afford α‐aminonitrile 2 in 85 % yield in a 53:47 dr. The presence of the α‐phenylethyl group as the chiral auxiliary ensured the control of the absolute configuration of the future C6 spiro‐center during the alkylation step of 2, which was carried out with 1‐bromo‐4‐chlorobutane. Next, elaboration of the 1‐azaspiro[5,5]undecane‐7‐one ring system was achieved in a two‐step sequence, involving (a) a Thorpe‐Ziegler annulation, and (b) the hydrolysis–decarboxylation of enaminonitrile (–)‐5 to afford spiroketone (+)‐6 in >99:1 dr. Finally, the incorporation of the future C7 butyl chain was carried out stereoselectively through a new reaction sequence which involved the synthesis of tricyclic oxazolidinone (–)‐11 and alkylation of the intermediary syn‐fluorohydrin (+)‐13 with nBuMgCl to form oxazolidinone (+)‐15 in an overall 19 % yield from (–)‐1.

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Section: Resultsmentioning

confidence: 99%

Formal Synthesis of (–)‐Perhydrohistrionicotoxin Using a Thorpe‐Ziegler Cyclization Approach. Synthesis of Functionalized Aza‐Spirocycles

Bouvry

Roisnel

et al. 2018

Eur J Org Chem

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“…Scheme 2 a) Reaction of PPh 3 with iodanes 5, 7, and 9 gives anhydride and benzoyl chloride products, and b) how this might be useful in the functionalization of alcohols Phosphoranes 2 15 and 4 16 are both known to effect deoxygenative halogenation of alcohols, but there are very limited examples of combining iodanes with phosphines to effect acylation reactions. 13 Given that PPh 3 is a strong nucleophile, and because little reaction is expected between iodanes and alcohols under these conditions, 13,17 intermediate A should still occur when phosphine activation by iodanes 5, 7, and 9 is carried out in the presence of alcohols (Scheme 2, b).…”

Section: Letter Syn Lettmentioning

confidence: 99%

Hypervalent Iodine-Based Activation of Triphenylphosphine for the Functionalization of Alcohols

Eljo

Carle

Murphy

2017

Synlett

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The use of hypervalent iodine reagents as a general tool for the activation of PPh3 and its application to the functionalization of alcohols is reported. Combination of PPh3 with PhICl2 or TolIF2 gives dihalophosphoranes that are characterized by 31P NMR, however, with PhIOAc2, PhI(OTFA)2, or the cyclic chloro(benzoyloxy)iodane, no phosphoranes were observed. Reaction of these iodanes with PPh3 in the presence of primary, secondary, or tertiary alcohols results in either halogenation or acyl-transfer products in moderate to high yield.

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Triphenylphosphine Dichloride

Cited by 2 publications

References 36 publications

Formal Synthesis of (–)‐Perhydrohistrionicotoxin Using a Thorpe‐Ziegler Cyclization Approach. Synthesis of Functionalized Aza‐Spirocycles

Formal Synthesis of (–)‐Perhydrohistrionicotoxin Using a Thorpe‐Ziegler Cyclization Approach. Synthesis of Functionalized Aza‐Spirocycles

Hypervalent Iodine-Based Activation of Triphenylphosphine for the Functionalization of Alcohols

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