Consecutive Cyclization of Allylaminoalkene by Intramolecular Aminolithiation−Carbolithiation

Tsuchida, Susumu; Kaneshige, Atsunori; Ogata, Tokutaro; Baba, Hiromi; Yamamoto, Yasutomo; Tomioka, Kiyoshi

doi:10.1021/ol801397v

Cited by 27 publications

(19 citation statements)

References 66 publications

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“…In a similar manner, a tandem aminolithiation/carbolithiation reaction allowed the efficient preparation of bicyclic octahydroindolizines and hexahydro-1H-pyrrolizines. When allylaminoalkene 76 was treated with n-BuLi in the presence of a bulky tert-butyltritylamine, the heterocycle 77 was isolated in 85% yield in high diastereomeric ratio (Scheme 11.21) [48]. The authors rationalized the stereochemical outcome of this reaction via the models previously proposed for the carbolithiation step [34,44,48].…”

Section: Intramolecular Carbolithiation Of Alkenesmentioning

confidence: 87%

Advances in Carbolithiation

Minko

Marek

2014

Lithium Compounds in Organic Synthesis

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Section: Intramolecular Carbolithiation Of Alkenesmentioning

confidence: 87%

Advances in Carbolithiation

Minko

Marek

2014

Lithium Compounds in Organic Synthesis

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“…All attempts to force the cyclization in this case by changing different reaction parameters did not lead to the desired products of intramolecular carbocyclization. It has been demonstrated that a sequential aminolithiation/carbolithiation reaction opens up an efficient route to bicyclic octahydroindolizines and hexahydro-1H-pyrrolizines [49]. When the allylaminoalkene 180 was treated with n-BuLi in the presence of a bulky tert-butyltritylamine, the heterocycle 181 was isolated in 85% yield (Scheme 10.59).…”

Section: N Phmentioning

confidence: 99%

“…The nature of the amine was rationalized by considering the reactivity of the plausible intermediate 183 toward protonation with the corresponding amine. The authors came to the conclusion that carbolithiation of 183 and protonation of less sterically hindered 184 with a bulky amine leads to the desired product of carbocyclization, while protonation of 182 with a less bulky amine leads to the side product [49]. Under the optimized conditions, product 181 was isolated as a 30 : 1 : 0 mixture of diastereomers, and the major diastereomer was determined to be trans,cis-181 by nOe experiments.…”

Section: N Phmentioning

confidence: 99%

“…Under the optimized conditions, product 181 was isolated as a 30 : 1 : 0 mixture of diastereomers, and the major diastereomer was determined to be trans,cis-181 by nOe experiments. Considering the models previously proposed for the carbolithiation step [43,45], the authors could rationalize the stereochemical outcome of this reaction [49]. The optimized conditions for the sequential aminolithiation/carbolithiation cyclization were applied to the synthesis of several other allyl-and homoallylaminoalkenes (Scheme 10.60).…”

Section: N Phmentioning

confidence: 99%

“…49 Proposed mechanism for the carboindation of terminal alkenes: anti attack of the nucleophile on an activated alkene substrate [40].…”

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confidence: 99%

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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.

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Consecutive Cyclization of Allylaminoalkene by Intramolecular Aminolithiation−Carbolithiation

Cited by 27 publications

References 66 publications

Advances in Carbolithiation

Advances in Carbolithiation

Carbometallation Reactions

Hydroamination of Alkenes

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