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Total syntheses of (+-)-cylindricine...

Liu, Tao.

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Total syntheses of (+-)-cylindricines A, D, and E, and (+-)-deoxypenostatin A. Synthetic approaches toward the syntheses of (+-)-penostatins A and B.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	Total syntheses of (+-)-cylindricines A, D, and E, and (+-)-deoxypenostatin A. Synthetic approaches toward the syntheses of (+-)-penostatins A and B./
Author:	Liu, Tao.
Description:	113 p.
Notes:	Adviser: Barry B. Snider.
Contained By:	Dissertation Abstracts International61-04B.
Subject:	Chemistry, Organic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9967594
ISBN:	0599723386

Total syntheses of (+-)-cylindricines A, D, and E, and (+-)-deoxypenostatin A. Synthetic approaches toward the syntheses of (+-)-penostatins A and B.
Liu, Tao.

Total syntheses of (+-)-cylindricines A, D, and E, and (+-)-deoxypenostatin A. Synthetic approaches toward the syntheses of (+-)-penostatins A and B. - 113 p.

Adviser: Barry B. Snider.

Thesis (Ph.D.)--Brandeis University, 2000.

The first total synthesis of cylindricine A (<bold>1.1a</bold>) has been accomplished by an efficient seven-step route in 10% overall yield. A double Michael addition of ammonia to dienone <bold>1.6</bold> provided 56% of the desired quinolinone <bold>1.5</bold>. Radical cyclization of chloroamine <bold> 1.40</bold> with CuCl and CuCl2 afforded 42% of cylindricine A (<bold>1.1a</bold>) and 41% of <italic>epi</italic>-cylindricine A (<bold> 1.41</bold>), which could be recycled to <bold>1.5</bold> by reduction with Zn in acidic MeOH. Reaction of <bold>1.1a</bold> with methoxide and acetate provided cylindricines D (<bold>1.1d</bold>) and E (<bold>1.1e</bold>), respectively.

ISBN: 0599723386Subjects--Topical Terms:

516206
Chemistry, Organic.

Total syntheses of (+-)-cylindricines A, D, and E, and (+-)-deoxypenostatin A. Synthetic approaches toward the syntheses of (+-)-penostatins A and B.
LDR:04002nam 2200289 a 45 001 938639
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020 $a 0599723386
035 $a (UnM)AAI9967594
035 $a AAI9967594
040 $a UnM $c UnM
100 1 $a Liu, Tao. $3 1262614
245 1 0 $a Total syntheses of (+-)-cylindricines A, D, and E, and (+-)-deoxypenostatin A. Synthetic approaches toward the syntheses of (+-)-penostatins A and B.
300 $a 113 p.
500 $a Adviser: Barry B. Snider.
500 $a Source: Dissertation Abstracts International, Volume: 61-04, Section: B, page: 1956.
502 $a Thesis (Ph.D.)--Brandeis University, 2000.
520 $a The first total synthesis of cylindricine A (<bold>1.1a</bold>) has been accomplished by an efficient seven-step route in 10% overall yield. A double Michael addition of ammonia to dienone <bold>1.6</bold> provided 56% of the desired quinolinone <bold>1.5</bold>. Radical cyclization of chloroamine <bold> 1.40</bold> with CuCl and CuCl2 afforded 42% of cylindricine A (<bold>1.1a</bold>) and 41% of <italic>epi</italic>-cylindricine A (<bold> 1.41</bold>), which could be recycled to <bold>1.5</bold> by reduction with Zn in acidic MeOH. Reaction of <bold>1.1a</bold> with methoxide and acetate provided cylindricines D (<bold>1.1d</bold>) and E (<bold>1.1e</bold>), respectively.
520 $a A short, convergent synthesis of deoxypenostatin A (<bold>2.30</bold>) was developed in 11 steps and 1.7% overall yield. In this scheme, a novel, stereoselective, intramolecular Diels-Alder reaction of a hydrated glyoxylate ester <bold>2.32</bold> catalyzed by Yb(OTf)3 was used as the key step to make lactone <bold>2.62</bold>. An intramolecular Horner-Emmons Wittig reaction was used to convert lactone <bold>2.62</bold> to enone <bold>2.70 </bold>. Epimerization with K2CO3 in methanol completed the total synthesis of <bold>2.30</bold>.
520 $a The total syntheses of penostatins A (<bold>2.1a</bold>) and B (<bold> 2.1b</bold>) were attempted using the method developed in the synthesis of deoxypenostatin A (<bold>2.30</bold>). A series of protected glyoxylate esters were synthesized and their intramolecular Diels-Alder reactions were examined. Treatment of ketal protected glyoxylate ester <bold>2.117</bold> with Yb(OTf) 3 gave the ketone glyoxylate ester <bold>2.129</bold>, which cyclized to give the DA product <bold>2.130</bold>. The stronger Lewis acid In(OTf) 3 or longer reaction times isomerized <bold>2.130</bold> to <bold>2.132 </bold>. Treatment of the <italic>cis</italic> methyl ether protected glyoxylate ester <bold>2.136</bold> with Yb(OTf)3 gave an inseparable mixture of DA product <bold>2.145</bold> and its isomer <bold>2.146</bold>. Treatment of the <italic>cis</italic> MEM ether protected glyoxylate ester <bold>2.152 </bold> with Yb(OTf)3 gave the hydroxyl glyoxylate ester <bold> 2.154</bold>, which cyclized to give an inseparable mixture of DA product <bold> 2.155</bold> and its isomer <bold>2.156</bold>. Adduct <bold>2.155</bold> is the desired precursor to penostatin A, so the mixture was converted to the TBS ether and treated with LiCH2PO(OMe)2 to form the separable hemiacetals <bold>2.159</bold> and <bold>2.160</bold>. The epimer <bold> 2.160</bold> was oxidized to diketophosphonate <bold>2.163</bold> and treated with base to effect the intramolecular Horner-Emmons Wittig reaction, which gave the TBS ether of bis <italic>epi</italic> penostatin A <bold>2.164</bold> in low yield. Unfortunately, a similar sequence on the desired isomer <bold> 2.159</bold> was unsuccessful under all conditions investigated.
590 $a School code: 0021.
650 4 $a Chemistry, Organic. $3 516206
690 $a 0490
710 2 0 $a Brandeis University. $3 1017415
773 0 $t Dissertation Abstracts International $g 61-04B.
790 $a 0021
790 1 0 $a Snider, Barry B., $e advisor
791 $a Ph.D.
792 $a 2000
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9967594