Cross-metathesis of allylcarboranes with O-allylcyclodextrins

Abstract

SummaryCross-metathesis between allylcarboranes and O-allylcyclodextrins was catalyzed by Hoveyda–Grubbs 2nd generation catalyst in toluene. The corresponding carboranyl-cyclodextrin conjugates were isolated in 15–25% yields.

Synthesis and supramolecular properties of regioisomers of mononaphthylallyl derivatives of γ-cyclodextrin

“…Mono 2 I - O -, 3 I - O - and 6 I - O -naphthylallyl-γ-CDs (2- O -NA-γ-CD, 2a , 3- O -NA-γ-CD, 2b , 6- O -NA-γ-CD, 2c ) were prepared from peracetylated O -allyl derivatives [ 14 ] by cross-metathesis with 2-vinylnaphthalene ( Scheme 1 ) in the presence of the Hoveyda–Grubbs 2nd generation catalyst. After deacetylation, column chromatography afforded the naphthylallyl derivatives in yields between 16–25%, which is comparable to the results of other metathesis reactions of allylated CDs [ 11 , 25 ]. In all cases, only the isomer with E configuration of the NA double bond was observed by 1 H NMR.…”

Monosubstituted Cyclodextrins as Precursors for Further Use

“…Allyl derivatives of CDs have been successfully applied in cross-metathesis [55][56][57] and, together with cinnamyl derivatives, could be oxidised to formylmethyl or carboxymethyl functional groups (see below). These derivatives could be then used for the Wittig reaction (so far applied only for formyl derivatives), [58][59][60] imine formation, [61,62] reductive amination [63] or the formation of amide bonds.…”

“…-CD α-D-glucopyranosyl 65.9 [86] 14 -CD 5,5,6,6,7,7,7-heptafluorohept-2-en-1-yl 67.77 [55] 15 -CD 4-{8,8′-μ-(sulfido)-[3,3′-commocobalt(III)-bis(1,2-di-68.28 [56] carbaundecaborate)]-8-yl}but-2-en-1-yl 16 -CD 5,6,6,6-tetrafluoro-5-(trifluoromethyl)hex-2-en-1-yl 67.78 [55] 17 -CD 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodec-2-en-1-yl 67.82 [55] 18 γ-CD allyl 67.58 [55] 19 γ-CD propargyl 67.5 [85] 20 γ-CD formylmethyl 69.7 [85] 21 γ-CD carboxymethyl 70.1 [85] 22 γ-CD 5,5,6,6,7,7,7-heptafluorohept-2-en-1-yl 67.79 [55] 23 γ-CD 5,6,6,6-tetrafluoro-5-(trifluoromethyl)hex-2-en-1-yl 67.81 [55] 24 γ-CD 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodec-2-en-1-yl 67.81 [55] Eur. …”

“…Unfortunately, this signal is thus overlapped with other peracetylated CD signals. However, this shift causes a decrease in the integral intensity of the H-3 signals by one ( Figure 5 [82] 2 α-CD cinnamyl 3.38 [82] 3 α-CD formylmethyl 3.34 [82] 4 α-CD carboxymethyl 3.43 [82] 5 -CD allyl 3.27 [83] 6 -CD allyl 3.28 [55] 7 -CD propargyl 3.55 [84] 8 -CD carboxymethyl 3.38 [83] 9 -CD 3,3-bis(chlorodimethylstannyl)propanyl 3.59 [84] 10 -CD 4-(1,2-dicarbadodecaboran-1-yl)but-2-en-1-yl 3.34 [56] 11 [56] dicarbaundecaborate)]-8-yl}but-2-en-1-yl 12 -CD 4-{8,8′-μ-(sulfido)-[3,3′-commocobalt(III)-bis(1,2-di-3.24 [56] carbaundecaborate)]-8-yl}but-2-en-1-yl 13 -CD 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodec-2-en-3.30 [55] 1-yl 14 γ-CD allyl 3.28 [85] 15 γ-CD propargyl 3.48 [85] 16 γ-CD formylmethyl 3.30 [85] 17 γ-CD carboxymethyl 3.43 [85] If none of the changes described above is observed, then the isomer is substituted in position 6. This could be confirmed by the measurement of APT or DEPT spectra.…”

“…A literature survey (of cases in which sufficient NMR spectroscopic data are given) confirmed that this method is usable with all known peracetylated mono-O-substituted α-, -and γ-CD derivatives ( Table 1, Table 2, and Table 3). H-2 A signals are shifted to the 3.2-3.6 ppm region, the integral inten- 1 α-CD allyl [82] 2 α-CD cinnamyl [82] 3 α-CD formylmethyl [82] 4 α-CD carboxymethyl [82] 5 α-CD 2-bromoprop-2-en-1-yl [82] 6 -CD allyl [83] 7 -CD allyl [56] 8 -CD cinnamyl [78] 9 -CD propargyl [84] 10 -CD carboxymethyl [78] 11 -CD 3,3-bis(chlorodimethylstannyl)propanyl [84] 12 -CD 4-(1,2-dicarbadodecaboran-1-yl)but-2-en-1-yl [56] 13 γ-CD allyl [85] 14 γ-CD propargyl [85] 15 γ-CD formylmethyl [85] 16 γ-CD carboxymethyl [85] [55] 2 α-CD cinnamyl 68.05 [82] 3 α-CD formylmethyl 70.20 [82] 4 α-CD 5,5,6,6,7,7,7-heptafluorohept-2-en-1-yl 68.33 [55] 5 α-CD 5,6,6,6-tetrafluoro-5-(trifluoromethyl)hex-2-en-1-yl 68.32 [55] 6 α-CD 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodec-2-en-1-yl 68.34 [55] 7 -CD allyl 67.6 [78] 8 -CD propargyl 67.67 [84] 9 -CD carboxymethyl 70.5 [78] 10 -CD 3,3-bis(chlorodimethylstannyl)propanyl 69.07 [84] 11 -CD 4-(1,2-dicarbadodecaboran-1-yl)but-2-en-1-yl 68.12 [56] 12…”