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R. R. Gadikota et al. / Tetrahedron: Asymmetry 14 (2003) 737-742 739 오 Lo -. LOWOH a, b 10. 16 FO c - Lo e, f L Ho OH TBDPSOBEHO IH RO 1, R = Ac 2, R=H Br, HO TOĦBE OH OH OH 5 Figure 1. Structures of trans-kumausyne 1, trans-deacetylkumausyne 2, srideema alhaj DAE - 0 X Share Comments AutoSave On H2O P O - Documenti Word Search File Home Insert Draw Design Layout Referenc

4. Draw the mechanism for the conversion of 11 to 12.

5. What is the side product in the conversion of 12 to 13?

What is the role of the potassium tert-butoxide in the conversion of 16 to 6?

8. What oxidizing agent is used to convert 17 into 18?

9. In the conversion of 17 to 18 why does the acetal form between C2-C3 and C5-C6 rather than

C4-C5 or C3-C4?

1. What are 4Å molecular sieves? (Used in synthesis of 11) (Cite your source)

2. How was 11 purified?

3. What is the appearance of 14?

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Answer #1

There are many subparts in this questions. I am answering the first four only (in order of appearance) (Chegg Policy: 1 questions per post or 4 sub parts in 1 question)

ANSWER Q-4: Mechanism 11 to 12

This is reaction to protect the alcohol group transforming it into an ester. The general reaction is:

pyridine, CH2Cl2 0 °C, 1h Hoot BzCI

And the mechanism is

20 HO0T C OT - Root pyridine

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ANSWER Q-5: side product of 12 to 13

The conversion of 12 to 13 involves the cleavage of the acetal, this is done with HCl and CH3OH. This conversion genertaes a side product: acetone.

HCI, CH3OH Reflux, 12 h MOCH3 Bz0 BzOOH Side product

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ANSWER Q-: role of potassium tert-butoxide in 16 to 6

The first step in conversion of 16 to 6 is a wittig reaction:

1) TMSCCCH2PPh3Br, t-BuOK, EtzО, -10°C 1h 2) NaOH, СН3ОН, rt, 2 h он

The tert-butoxide is used to transform the TMSCCCH2PPh3Br (3-(trimethylsilyl-2-propynyl)- triphenyl phosphonium bromide) into the ylide needed to wittig reaction. The tert-butoxide is a strong base and a weak nucleophile, this allows the formation of ylide

Ph. Ph Phi Phi Pro CH3 -si-CH3 oot CH3 -si-CH3

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ANSWER Q-8: oxidazing agent in conversion 17 to 18

Conversion of 17 to 18 involves a first step of protection of OH group in the ring and the side chain by formation of an acetal. This cause the reduction of ring. Then, in the second step, the anomeric carbon is oxidized to a ketone. This reaction is done using PCC as oxidazing agent because this is useful to oxidized anomeric carbons:

ОН Ко, ОН 1) acetone, H2SO4, CuSO4, 1, 12h 2) PCC, CH2Cl2 reflux, 3h OH HOY Он

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