Synthesis of 3-Quinuclidinyl Benzilate Derivatives

Kabalka, George W.; Mathur, S. B.; Gai, Y.-Z.

doi:10.1080/00304949009356671

Cited by 2 publications

(1 citation statement)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A key lead for O -alkylating the trimethylsiloxyl group of enone-derived 17 cyanohydrins stems from two O -alkylations of trimethylsilyl cyanohydrins with ClCH 2 OCH 3 . Presuming the alkylation to require a particularly reactive electrophile, the cyanohydrin 5a 17a,b was treated with the sulfonium ylide 9a 19 to directly generate the methylthiomethyl cyanohydrin 6a (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Cyclic Alkenenitriles: Synthesis, Conjugate Addition, and Stereoselective Annulation

et al. 2003

View full text Add to dashboard Cite

O-Alkylation of unsaturated silyl cyanohydrins with DMSO-Ac2O triggers a rearrangement to methylthiomethyl-protected hydroxyalkenenitriles that are easily hydrolyzed for subsequent annulations with omega-chloroalkyl Grignard reagents. Deprotonating the gamma-hydroxyalkenenitriles with t-BuMgCl followed by addition of omega-chloroalkyl Grignard reagents triggers a conjugate addition-alkylation sequence leading exclusively to cis-octalins, hydrindanes, and decalins. Stereoelectronic control favors an axial conjugate addition leading to a particularly reactive conformer that rapidly cyclizes to cis-fused bicyclic nitriles, whereas generating the ring-flipped conformer, through a stepwise sequence, allows access to the diastereomeric trans-decalin. Collectively, the rearrangement-annulation sequence represents the first general annulation of alkenenitriles to assemble diverse bicyclic nitriles with complete control over the two newly installed stereocenters.

show abstract

Section: Resultsmentioning

confidence: 99%