KBS22-2 - Linear click coupling of bis-propargyl diaminohexane and azidoadamantane

[KlementineJBS]

Link to HIRAC, original method and previous attempt #29

KBS22 Linear amine click coupling with azidoadamantane.docx

Reaction scheme

Outcome

[KlementineJBS]

30.04.24

1. Added NaAsc (52 mg, 1 equiv.), CuI (9 mg, equiv.) and 1-azidoadamantane (95.7 mg, 0.540 mmol, 2.3 equiv.) to a flask
2. Backfilled and evacuated x 5
3. Added KBS17 (93 mg, 0.237 mmol) dissolved in sparged THF (3 mL)
4. added sparged water (3 mL)
5. Left stirring from 4 pm

[KlementineJBS]

Crude LRMS

Evidence of desired product at 747.53+ [M+H]+ and 769.52+ [M+Na]+. Seems likely that 761.55- is related?

Also signs of unwanted products - 633.40+, 600.42-, but these haven't been identified. No obvious sign of SM (usually seen as 415+) or singly clicked product (mass of 531).

Will work up shortly.

KBS22-2 RM.d.zip KBS22-2 RM.pdf

[KlementineJBS]

01.05.24

Worked up as TLC and MS both indicated consumption of SM. (TLC is 5% MeOH in DCM with ammonium.)

<img width="350 src="https://github.com/KlementineJBS/USYD_PhD_ELN/assets/78768991/4b2ac422-4d25-4e7c-862b-efbcdb6142c8">

6. Quenched with 15 mL ammonium chloride solution
7. Extracted with DCM 3 x 20 mL
8. Washed with EDTA solution (25 mM, 25 mL)
9. Washed with brine + dried over mag sulphate

[KlementineJBS]

H NMR

Product clearly evident but seems to be almost 1:3 ratio of desired product:singly clicked product. Frustrating.

nmr300_20240501_KBS22-2 cr_1.zip KBS22-2 cr.pdf

[KlementineJBS]

LRMS

KBS22-2 crude.d.zip KBS22-2 crude.pdf

[KlementineJBS]

Decided to react again with more azidoadamantane.