An isotope effect study of triple bond participation during a homopropargyl rearrangement

Collins, Clair J.; Benjamin, Ben M.; Hanack, Michael; Stutz, H.

doi:10.1021/ja00447a077

Cited by 14 publications

(3 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…While there exist a number of examples for 3‐exo/4‐endo‐dig closure onto carbocations, products are only observed in the presence of suitable nucleophiles . The bond‐breaking and bond‐forming events were found to be asynchronous, and the regioselectivity of these closures is determined by the substituents of the alkyne (Figure ) …”

Section: Extension 4: Promoted Cyclizationsmentioning

confidence: 99%

The Baldwin rules: revised and extended

Gilmore

Mohamed

Alabugin

2016

WIREs Comput Mol Sci

136

View full text Add to dashboard Cite

The Baldwin rules constitute one of the clearest examples of the success which can be obtained through the application of stereoelectronic concepts to reaction design. With thousands of examples, the predictive power of these rules is inarguable. However, time has revealed a number of exceptions and gray areas within these rules, leading to extensions and revisions. In this review, we will present an overview of how subsequent studies of ring closure have clashed with several of Baldwin's predictions, leading to the revision of some classes of ring closure (alkyne cyclizations, electrophilic closures, etc.). We also discuss for which the original rules were vague (epoxides) or absent (promoted cyclizations), and the evidence revealed since Baldwin's work that has allowed for a better understanding of these ambiguities. With the concise summation of these amendments, this review aims to present an overview of the understanding of cyclization reactions to date. For further resources related to this article, please visit the WIREs website

show abstract

Section: Extension 4: Promoted Cyclizationsmentioning

confidence: 99%

The Baldwin rules: revised and extended

Gilmore

Mohamed

Alabugin

2016

WIREs Comput Mol Sci

136

View full text Add to dashboard Cite

show abstract

“…210 The mechanism of the homopropargyl rearrangement has been determined based on the investigation of the solvolysis of functionally substituted alkylidenecyclopropanes 22 and cyclobutenes 211 as well as various open-chain and cyclic propargyl derivatives. 212,213 Studies of isotope effects involved in the solvolysis 121 and stereochemical aspects of the rearrangements of chiral pentynyl triflates 214 have also been invoked. The results of these studies led to the conclusion that the solvolysis directly proceeds to the cations 428 and 429 via a transition state typical of S N 2 type reactions.…”

Section: Alkynyl Carbocations With a Remote Triple Bondmentioning

confidence: 99%

“…The results of these studies led to the conclusion that the solvolysis directly proceeds to the cations 428 and 429 via a transition state typical of S N 2 type reactions. 27,121,210 However, it has been shown for the solvolysis of cyclobut-1-enyl nonaflates 434 in trifluoroethanol that the presence of substituents stabilising the cationic centre at the 3-position of the ring is favourable for the formation of…”

Section: Alkynyl Carbocations With a Remote Triple Bondmentioning

confidence: 99%

Alkynylcarbenium ions and related unsaturated cations

Lukyanov¹,

Koblik²,

Muradyan³

1998

Russ. Chem. Rev.

View full text Add to dashboard Cite

Mechanistische und präparative Aspekte der Chemie der Vinylkationen

Hanack

1978

Angewandte Chemie

Self Cite

View full text Add to dashboard Cite

In den letzten Jahren ist umfangreiches experimentelles Material erschlossen worden, das zwingend auf Vinylkationen als Zwischenstufen deutet. Vinylkationen können durch elektrophile Additionen an Alkine und Allene sowie unter Beteiligung dieser Gruppierungen bei Solvolysereaktionen erzeugt werden. Die heterolytische Bindungsspaltung von Vinylverbindungen führt ebenfalls zu Vinylkationen. Beispiele für präparative Anwendungen sind Synthesen von substituierten Indenen, Cyclobutanonen und Cyclopropylketonen.

show abstract

An isotope effect study of triple bond participation during a homopropargyl rearrangement

Cited by 14 publications

References 0 publications

The Baldwin rules: revised and extended

The Baldwin rules: revised and extended

Alkynylcarbenium ions and related unsaturated cations

Mechanistische und präparative Aspekte der Chemie der Vinylkationen

Contact Info

Product

Resources

About