Efficient synthesis of 1-(trialkylstannyl)- and 1-(triarylstannyl)bicyclo[1.1.1]pentanes

Toops, Dana S.; Barbachyn, Michael R.

doi:10.1021/jo00075a063

Cited by 21 publications

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“…A more efficient synthesis of 9 via lithium‐metalloid exchange was reported by Barbachyn and co‐workers in 1993 (Scheme B) . Treating bicyclo[1.1.1]pentan‐1‐yltributylstannane ( 11 ) with n ‐butyllithium ( n BuLi) afforded the desired intermediate 9 exclusively . The most common pathway to achieve alkyllithium species by lithium‐halogen exchange proved most challenging as demonstrated by Della and co‐workers (Scheme C) .…”

Section: Syntheses Of 1‐substituted Bcpsmentioning

confidence: 95%

“…A 2 : 1 mixture of BCP−Li ( 9 ) and sulfide 10 were obtained, reducing the maximum yield of the electrophile adduct to 67% . A more efficient synthesis of 9 via lithium‐metalloid exchange was reported by Barbachyn and co‐workers in 1993 (Scheme B) . Treating bicyclo[1.1.1]pentan‐1‐yltributylstannane ( 11 ) with n ‐butyllithium ( n BuLi) afforded the desired intermediate 9 exclusively .…”

Section: Syntheses Of 1‐substituted Bcpsmentioning

confidence: 99%

“…The only exception is that 1‐chlorobicyclo[1.1.1]pentane ( 12 ), the inactive analogue, could be achieved in 1 step from 2 by hydrogen atom transfer chemistry . Although neither 8 nor 11 is commercially available, both could be readily prepared from 2 in 1 step with 99% and 93% isolated yields, respectively. Additionally, the lithium‐metalloid exchange process (Scheme B) exclusively forms the desired intermediate 9 , which is superior than the LiDBB reduction process (Scheme A).…”

Section: Syntheses Of 1‐substituted Bcpsmentioning

confidence: 99%

“…As a close relative of Schmidt reaction, a variation of Hofmann rearrangement was utilized in the synthesis of 15 N labeled 21⋅HCl (reported by Della and co‐workers, Scheme C) . In 1993, Barbachyn and co‐workers reported the first synthetic strategy to achieve 21 without the intermediacy of carboxylic acid 18 (Scheme D) . In this work, BCP−Li ( 9 ), generated by lithium‐metalloid exchange from 11 , was converted directly to 21 using lithium methoxyamide (generated from treatment of methoxyamine and methyllithium) as the electrophile .…”

Section: Syntheses Of 1‐substituted Bcpsmentioning

confidence: 99%

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Selected Topics in the Syntheses of Bicyclo[1.1.1]Pentane (BCP) Analogues

Pham

2019

Asian J Org Chem

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Section: Syntheses Of 1‐substituted Bcpsmentioning

confidence: 95%

Section: Syntheses Of 1‐substituted Bcpsmentioning

confidence: 99%

Section: Syntheses Of 1‐substituted Bcpsmentioning

confidence: 99%

Section: Syntheses Of 1‐substituted Bcpsmentioning

confidence: 99%

See 2 more Smart Citations

Selected Topics in the Syntheses of Bicyclo[1.1.1]Pentane (BCP) Analogues

Pham

2019

Asian J Org Chem

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“…The instability of the parent compound (3, X \ H) has also been noted. 13 Finally, we should mention that our attempts to prepare halogen derivatives of 3 (X \ F, Cl and I) were unsuccessful. Trimethylstannylation (method A) of 1-bromo-3-Ñuoro-,9 1-iodo-3-Ñuoro-37 and 1,3-diiodobicyclo[1.1.1]pentanes34 gave only [1.1.1]propellane as the primary product.…”

Section: Coupling Constantsmentioning

confidence: 99%

Through-space transmission of polar substituent effects in the bicyclo[1.1.1]pentane ring system as monitored by119Sn NMR chemical shifts: a13C and119Sn NMR study of 3-substituted-(X)bicyclo[1.1.1]pent-1-yltrimethylstannanes

Adcock

Krstic

1997

Magn. Reson. Chem.

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A series of 3‐substituted(X)bicyclo[1.1.1]pent‐1‐yltrimethylstannanes (3) were synthesized and their 119Sn and 13C NMR spectra were recorded. The 119Sn substituent chemical shifts (SCS) and the one‐bond carbon–tin coupling constants [1J(13C,119Sn)] were analyzed in terms of possible substituent–probe interactions. The study clearly reveals that the 119Sn NMR parameters of 3 are remarkably sensitive to modulation of the through‐space back‐ or rear‐lobe interactions between the bridgehead bond molecular orbitals by the electronic character of the substituent. An extraordinarily large four‐bond tin–tin coupling constant in 3 (X=SnMe3) highlights the significance of through‐space bridgehead–bridgehead interactions in this system. © 1997 John Wiley & Sons, Ltd.

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Experimental and theoretical study of substituent effects on3J(13C1-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes

Della¹,

Lochert²,

Peruchena³

et al. 1996

J. Phys. Org. Chem.

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A series of 23 bridgehead-substituted bicyclo[l.l.l]pentanes were synthesized and the 3J(Cl-H) coupling constants determined from their proton-coupled I3C NMR spectra. It was found that the values of the couplings are strongly dependent upon the type of substituent present, with powerful effects exerted by the halogens in particular. The IPPP-CLOPPA-INDO theoretical approach, which was employed to provide a measure of the extent of through-bond versus through-space transmission of coupling information, was found to give 3J(Cl-H) values in good agreement with experimental data. Empirical substituent parameter regressions were performed and found to be consistent with the CLOPPA description of the increase in both the through-bond and through-space contributions to the coupling. The substituent parameter regressional analyses also demonstrated that electronegativity effects play a predominant role in determining the magnitude of the couplings, particularly in those substrates in which the substituent is attached to the ring system by a secondrow element.

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Efficient synthesis of 1-(trialkylstannyl)- and 1-(triarylstannyl)bicyclo[1.1.1]pentanes

Cited by 21 publications

References 0 publications

Selected Topics in the Syntheses of Bicyclo[1.1.1]Pentane (BCP) Analogues

Selected Topics in the Syntheses of Bicyclo[1.1.1]Pentane (BCP) Analogues

Through-space transmission of polar substituent effects in the bicyclo[1.1.1]pentane ring system as monitored by119Sn NMR chemical shifts: a13C and119Sn NMR study of 3-substituted-(X)bicyclo[1.1.1]pent-1-yltrimethylstannanes

Experimental and theoretical study of substituent effects on3J(13C1-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes

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