KBS18-2 - Click coupling of bis-propargyl cyclam and azidomethylferrocene

[KlementineJBS]

Link to HIRAC, original method and master page

Previous attempt is #20

Reaction scheme

Outcome

[KlementineJBS]

1. Added copper sulphate pentahydride (15.1 mg, 0.060 mmol, 0.2 equiv.), sodium ascorbate (25.5 mg, 0.129 mmol, 0.5 equiv.) and KBS10 (120.7 mg, 0.253 mmol) to a flask
2. Evacuated and backfilled with nitrogen (x5)
3. Added KBS16 (132 mg, 0.549 mmol, 2.2 equiv.) dissolved in sparged THF (5 mL)
4. Added sparged water (5 mL)
5. Left stirring from 11.45 am

[KlementineJBS]

07.03.23

TLC was ambiguous - only one set of spots showed up strongly by UV, but ninhydrin revealed some more spots that potentially indicate mono product. SM appeared to be completely consumed.

'

5% MeOH in DCM

Took reaction off stirring and left to evaporate THF overnight.

[KlementineJBS]

08.03.23

Added 10 mL NH4Cl and stirred 10 minutes. Extracted with DCM (3 x 15 mL) and washed with brine (40 mL) before drying over magnesium sulphate.

Vial: 15.8230 Full vial: 16.1683 Mass: 345.3 mg (0.36 mmol)

[KlementineJBS]

NMR

KBS18-2 cr_1.zip KBS18-2 crude.pdf

Looks OK compared to #20. Need to column and do more characterisation.

[KlementineJBS]

13.03.23

LRMS

KBS18-2 cr.pdf KBS18-2 cr.d.zip

Peak at 959.43 [M+H]+.

[KlementineJBS]

[KlementineJBS]

20.03.23

F1-3 appears to have nothing worthwhile. F4-14 looks like good product. F15-21 appears to be product but quite dilute. It may also contain some mono-click coupled product, as there are two boc peaks (indicating split environments).

KBS18-2 F1-3_1.zip KBS18-2 F4-14_1.zip KBS18-2 F15-21_1.zip KBS18-2 F1-21.pdf