Double FLP-Alkyne Exchange Reactions: A Facile Route to Te/B Heterocycles

Tsao, Fu An; Cao, Levy L.; Stephan, Douglas W.

doi:10.1021/jacs.5b09526

Cited by 33 publications

(17 citation statements)

References 35 publications

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“…1,2,4 The reactivity of the alkynes depends on the C≡C bond nature and where the C≡C bond reactivity is usually influenced by its substituents. Currently, only a handful of (F)LP–alkyne cycloadditions to zwitterionic heterocycloalkenes of A, 7,8 B, 9 C, 10 D, 11 and E 5,6 types have been documented (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

N-Geminal P/Al Lewis Pair–Alkyne Dipolar Cycloaddition to the Zwitterionic C₂PNAl-Heterocyclopentene

Ding

et al. 2017

ACS Omega

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The N-geminal P/Al Lewis pair [Ph 2 PN(2,6- i Pr 2 C 6 H 3 )AlEt 2 ] 2 ( 1 ) has been prepared and studied for reaction with a series of alkynes. The reaction of 1 with RC≡CR yielded zwitterionic C 2 PNAl-heterocyclopentene [Ph 2 ⌜ PN(2,6- i Pr 2 C 6 H 3 )AlEt 2 ](CR= ⌝ CR) (R = Me ( 2 ), Ph ( 3 )); with PhC≡CEt produced two isomers, [Ph 2 ⌜ PN(2,6- i Pr 2 C 6 H 3 )AlEt 2 ](CPh= ⌝ CEt) ( 4a ) and [Ph 2 ⌜ PN(2,6- i Pr 2 C 6 H 3 )AlEt 2 ](CEt= ⌝ CPh) ( 4b ); and with other alkynes generated [Ph 2 ⌜ PN(2,6- i Pr 2 C 6 H 3 )AlEt 2 ](CR 1 = ⌝ CR 2 ) (R 1 , R 2 = CO 2 Et, Ph ( 5 ); SiMe 3 , Ph ( 6 ); PPh 2 , Ph ( 7 ); SiMe 3 ,H ( 8 ); H, EtO ( 9 )). Natural bond orbital analysis of the charge separation of the C≡C bond of alkynes was carried out, and then, the electronic matching interaction mode between the combined Lewis acid (AlEt 2 ) and base (PPh 2 ) groups of 1 and the C≡C bond of such alkynes was discussed. Reactions of 1 with alkene, nitrile, and carbodiimide molecules were also carried out, and cycloaddition compounds 10 – 12 were produced.

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Section: Introductionmentioning

confidence: 99%

N-Geminal P/Al Lewis Pair–Alkyne Dipolar Cycloaddition to the Zwitterionic C₂PNAl-Heterocyclopentene

Ding

et al. 2017

ACS Omega

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“…A significant relevant example showed that 1-bora-4-tellurocyclohexa-2,5-diene undergoes subsequent [4+2] cycloaddition/alkyne-elimination via a Te/B FLP-type mechanism, reported by Stephan et al . 56 . These results prompted us to examine the thermal stability of the [4+2] cycloadducts 7 and 8 .…”

Section: Discussionmentioning

confidence: 99%

Ambiphilic boron in 1,4,2,5-diazadiborinine

Wang

Ganguly

et al. 2016

Nat Commun

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Boranes have long been known as the archetypal Lewis acids owing to an empty p-orbital on the boron centre. Meanwhile, Lewis basic tricoordinate boranes have been developed in recent years. Here we report the synthesis of an annulated 1,4,2,5-diazadiborinine derivative featuring boron atoms that exhibit both Lewis acidic and basic properties. Experimental and computational studies confirmed that two boron atoms in this molecule are spectroscopically equivalent. Nevertheless, this molecule cleaves C–O, B–H, Si–H and P–H bonds heterolytically, and readily undergoes [4+2] cycloaddition reaction with non-activated unsaturated bonds such as C=O, C=C, C≡C and C≡N bonds. The result, thus, indicates that the indistinguishable boron atoms in 1,4,2,5-diazadiborinine act as both nucleophilic and electrophilic centres, demonstrating ambiphilic nature.

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“…71 Thus, N-t-Bu-BN indole 41 is more nucleophilic in EAS than its carbonaceous counterpart and displays the classical indole-type regioselectivity (i.e., at the 3-position) (Scheme 8). 74 More recently, the same authors demonstrated further reactivity of these heterocycles, providing access to unsymmetrically substituted tellurium-boron based heterocycle. 75 Unusual reactivity has been noted for 1,3,2,5-diazadiborine 45 containing a formal B(+ 1)/B(+ III) mixed valence system in the aromatic six-membered B 2 C 2 N 2 ring.…”

Section: Scheme 3 Schemementioning

confidence: 97%

Six-Membered Rings With Two or More Heteroatoms With at Least One Boron

Sotiropoulos

Romanenko

2022

Comprehensive Heterocyclic Chemistry IV

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Double FLP-Alkyne Exchange Reactions: A Facile Route to Te/B Heterocycles

Cited by 33 publications

References 35 publications

N-Geminal P/Al Lewis Pair–Alkyne Dipolar Cycloaddition to the Zwitterionic C₂PNAl-Heterocyclopentene

N-Geminal P/Al Lewis Pair–Alkyne Dipolar Cycloaddition to the Zwitterionic C₂PNAl-Heterocyclopentene

Ambiphilic boron in 1,4,2,5-diazadiborinine

Six-Membered Rings With Two or More Heteroatoms With at Least One Boron

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Double FLP-Alkyne Exchange Reactions: A Facile Route to Te/B Heterocycles

Cited by 33 publications

References 35 publications

N-Geminal P/Al Lewis Pair–Alkyne Dipolar Cycloaddition to the Zwitterionic C2PNAl-Heterocyclopentene

N-Geminal P/Al Lewis Pair–Alkyne Dipolar Cycloaddition to the Zwitterionic C2PNAl-Heterocyclopentene

Ambiphilic boron in 1,4,2,5-diazadiborinine

Six-Membered Rings With Two or More Heteroatoms With at Least One Boron

Contact Info

Product

Resources

About

N-Geminal P/Al Lewis Pair–Alkyne Dipolar Cycloaddition to the Zwitterionic C₂PNAl-Heterocyclopentene

N-Geminal P/Al Lewis Pair–Alkyne Dipolar Cycloaddition to the Zwitterionic C₂PNAl-Heterocyclopentene