Synthesis of (−)-Sedinine by Allene Cyclization and Iminium Ion Chemistry

Bates, Roderick W.; Lu, Yongna

doi:10.1021/ol1016492

Cited by 45 publications

(28 citation statements)

References 61 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Although the focus of this review is on silver-catalysed reactions, the reaction of silver with allenols and amino allenes using stoichiometric amounts of the metal has been known since the 55 1980's, and therefore examples of those reactions have been included in this review for a wider understanding of this transformation.…”

Section: Silvermentioning

confidence: 99%

“…5 δ-Monoalkyl and δ,δ-dialkyl substituted α-allenols gave 2,5-dihydrofurans by 5-endo attack to the distal double bond, when reacted in the presence of 3 mol% of AgBF 4 in CHCl 3 (Scheme 3a). However, 55 unsubstituted derivatives needed harsher conditions (10 mol% of silver nitrate in mixtures of water/acetone, in the presence of CaCO 3 ) to afford the products in moderate yields (Scheme 3b).…”

Section: Intramolecular Addition Of O-hmentioning

confidence: 99%

“…5 They reported that these substrates needed the more active conditions (10 mol% of silver nitrate in mixtures of water/acetone in the presence of CaCO 3 ) to afford 5,6-dihydro-2H-pyrans (Scheme 25). Formation of six-membered rings is favoured here by attack of the oxygen to 55 the terminal carbon of the distal double bond of the allene in a 6-endo cyclisation.…”

mentioning

confidence: 99%

“…More recently, Hii et al exploited the enantioselective version of 55 the reaction using complexes of silver with chiral counterions derived from oxophosphorous(V) phosphinate (β-CgPOOH) and phosphate (TADDOL-POOH, see Scheme 29). 32 In comparison with the reaction of the oxygen derivatives, γ-amino allenes gave slower reactions, probably due to slow proton transfer after 60 cyclisation (see Scheme 28).…”

mentioning

confidence: 99%

“…However, reaction with the TADDOL derivative and pyridine was inhibited. The group of Bates et al has used extensively the silver-catalysed cyclisation of allenic hydroxylamine derivatives in the total synthesis of piperidine alkaloids, such us sedamine (Scheme 47a), 54 sedinine (Scheme 47b), 55 porantheridine (Scheme 47c), 56 10 and nupharamine (Scheme 47d). 57 The vinyl pyrrolidine is obtained in all the cases, and then expanded by breaking the N-O bond with the construction of the 6-memebred ring present in the natural product by different methods in each case.…”

mentioning

confidence: 99%

See 4 more Smart Citations

Silver and platinum-catalysed addition of O–H and N–H bonds to allenes

Muñoz¹

2014

Chem. Soc. Rev.

188

View full text Add to dashboard Cite

5Transition-metal catalysed nucleophile addition to allenes is a very powerful tool for the synthesis of functionalised molecules containing heteroatoms, heterocycles in the intramolecular version, or allyl derivatives in the intermolecular. The reaction has been explored with a wide variety of metals, being silver one of the most effective. Although platinum has somehow been less explored, different reactivity has been observed with this metal, showing the great potential and versatility of this methodology. This 10 review will highlight the reactions with these two metals, silver and platinum, when oxygen or nitrogen nucleophiles are employed. Although most of the examples describe the intramolecular version, some intermolecular reactions have been described with platinum, and will also be covered.

show abstract

Section: Silvermentioning

confidence: 99%

Section: Intramolecular Addition Of O-hmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Silver and platinum-catalysed addition of O–H and N–H bonds to allenes

Muñoz¹

2014

Chem. Soc. Rev.

188

View full text Add to dashboard Cite

show abstract

Hydroamination of Alkenes

Reznichenko

Hultzsch

2015

Organic Reactions

View full text Add to dashboard Cite

The addition of an amine NH‐functionality to alkenes (including vinyl arenes, conjugated dienes, allenes or ring‐strained alkenes), the so‐called hydroamination, represents a simple and highly atom‐economical approach for the synthesis of nitrogen‐containing products. A large variety of catalyst systems are available, ranging from alkali, alkaline earth, rare earth, Group 4 and Group 5 metals, to late transition metal catalysts, and, less prominent, Brønsted and Lewis acid‐based catalyst systems. The mode of operation of these catalyst systems can vary significantly and the different reaction mechanisms and the scope and limitations are discussed. While intramolecular hydroamination reactions can be readily achieved with a large number of catalyst systems, significantly fewer examples for the more challenging intermolecular hydroamination are known, especially for unactivated alkenes. The stereoselective hydroamination has also received significant attention due to the importance of chiral nitrogen‐containing molecules in pharmaceutical industry. A variety of highly selective chiral catalyst systems have been developed for intramolecular hydroaminations, while examples of intermolecular asymmetric hydroaminations are scarce. Hydroamination in the context of this review article is defined as the addition of HNR 2 across a non‐activated, unsaturated carbon‐carbon multiple bond. This review focuses on the hydroamination reaction of simple, non‐activated alkenes. The addition of amines to slightly activated alkenes, such as vinyl arenes, 1,3‐dienes, strained alkenes (norbornene derivatives, methylenecyclopropenes) and allenes is closely related and is covered as well. However, hydroamination reactions of alkynes and Aza‐Michael reactions involving the addition of an N‐H fragment across the conjugated or otherwise activated double bond of a Michael acceptor are not covered. The scope of amine types includes ammonia, primary and secondary aliphatic and aromatic amines, azoles, and hydrazines. N ‐Protected amines, such as ureas, carboxamides, and sulfonamides are covered as well, as they are important substrates for metal‐free and late transition metal‐based catalysts. The literature through January 2011 will be covered with two selected references from 2012 (comprising Table 3D). A supplemental reference list is provided for reports appearing February 2011 through April 2015. The chapter is organized by the nature of the carbon unsaturation to which the amine is added. Ranging from less reactive substrates such as ethylene and unactivated alkenes, to slightly activated substrates, such as vinyl arenes, and more activated substrates, including conjugated dienes, allenes and strained alkenes. Enantioselective hydroamination reactions, an area that has seen significant progress over the past decade, are discussed next. Finally, tandem hydroamination/carbocyclization reactions of aminodialkenes provide rapid access to complex alkaloidal skeletons. The tables at the end of the chapter are separated into five main sections: achiral intermolecular hydroamination, achiral intramolecular hydroamination, enantioselective intermolecular hydroamination, enantioselective intramolecular hydroamination, and tandem hydroamination/carbocyclization. Within the first four sections the tables are further divided into subsections based on the participating alkene, i.e. alkenes, vinyl arenes, dienes, allenes, and strained alkenes.

show abstract

Electrophilic Alkene and Alkyne Complexes

Bates

2012

Organic Synthesis Using Transition Metals

View full text Add to dashboard Cite

Synthesis of (−)-Sedinine by Allene Cyclization and Iminium Ion Chemistry

Cited by 45 publications

References 61 publications

Silver and platinum-catalysed addition of O–H and N–H bonds to allenes

Silver and platinum-catalysed addition of O–H and N–H bonds to allenes

Hydroamination of Alkenes

Electrophilic Alkene and Alkyne Complexes

Contact Info

Product

Resources

About