&lt;!--[if gte vml 1]&gt;&lt;v:shapetype id="_x0000_t75" coordsize="21600,21600" o:spt="75" o:preferrelative="t" path="m@4@5l@4@11@9@11@9@5xe" filled="f" stroked="f"&gt; &lt;v:stroke joinstyle="miter"/&gt; &lt;v:formulas&gt; &lt;v:f eqn="if lineDrawn pixelLineWidth 0"/&gt; &lt;v:f eqn="sum @0 1 0"/&gt; &lt;v:f eqn="sum 0 0 @1"/&gt; &lt;v:f eqn="prod @2 1 2"/&gt; &lt;v:f eqn="prod @3 21600 pixelWidth"/&gt; &lt;v:f eqn="prod @3 21600 pixelHeight"/&gt; &lt;v:f eqn="sum @0 0 1"/&gt; &lt;v:f eqn="prod @6 1 2"/&gt; &lt;v:f eqn="prod @7 21600 pixelWidth"/&gt; &lt;v:f eqn="sum @8 21600 0"/&gt; &lt;v:f eqn="prod @7 21600 pixelHeight"/&gt; &lt;v:f eqn="sum @10 21600 0"/&gt; &lt;/v:formulas&gt; &lt;v:path o:extrusionok="f" gradientshapeok="t" o:connecttype="rect"/&gt; &lt;o:lock v:ext="edit" aspectratio="t"/&gt;&lt;/v:shapetype&gt;&lt;v:shape id="_x0000_s1027" type="#_x0000_t75" style='position:absolute; margin-left:-31.5pt;margin-top:-11.25pt;width:417.8pt;height:58.55pt; z-index:251658240;mso-position-horizontal-relative:text; mso-position-vertical-relative:text'&gt; &lt;v:imagedata src="file:///C:\Users\mdrahman\AppData\Local\Temp\1\msohtmlclip1\01\clip_image001.emz" o:title=""/&gt; &lt;w:wrap type="square"/&gt;&lt;/v:shape&gt;&lt;![if gte mso 9]&gt;&lt;o:OLEObject Type="Embed" ProgID="ChemDraw.Document.6.0" ShapeID="_x0000_s1027" DrawAspect="Content" ObjectID="_1475311855"&gt;&lt;/o:OLEObject&gt;&lt;![endif]&gt;&lt;![endif]--&gt;&lt;!--[if !vml]--&gt;&lt;!--[endif]--&gt;&lt;!--[if gte vml 1]&gt;&lt;v:shapetype id="_x0000_t75" coordsize="21600,21600" o:spt="75" o:preferrelative="t" path="m@4@5l@4@11@9@11@9@5xe" filled="f" stroked="f"&gt; &lt;v:stroke joinstyle="miter"/&gt; &lt;v:formulas&gt; &lt;v:f eqn="if lineDrawn pixelLineWidth 0"/&gt; &lt;v:f eqn="sum @0 1 0"/&gt; &lt;v:f eqn="sum 0 0 @1"/&gt; &lt;v:f eqn="prod @2 1 2"/&gt; &lt;v:f eqn="prod @3 21600 pixelWidth"/&gt; &lt;v:f eqn="prod @3 21600 pixelHeight"/&gt; &lt;v:f eqn="sum @0 0 1"/&gt; &lt;v:f eqn="prod @6 1 2"/&gt; &lt;v:f eqn="prod @7 21600 pixelWidth"/&gt; &lt;v:f eqn="sum @8 21600 0"/&gt; &lt;v:f eqn="prod @7 21600 pixelHeight"/&gt; &lt;v:f eqn="sum @10 21600 0"/&gt; &lt;/v:formulas&gt; &lt;v:path o:extrusionok="f" gradientshapeok="t" o:connecttype="rect"/&gt; &lt;o:lock v:ext="edit" aspectratio="t"/&gt;&lt;/v:shapetype&gt;&lt;v:shape id="_x0000_s1027" type="#_x0000_t75" style='position:absolute; margin-left:-31.5pt;margin-top:-11.25pt;width:417.8pt;height:58.55pt; z-index:251658240;mso-position-horizontal-relative:text; mso-position-vertical-relative:text'&gt; &lt;v:imagedata src="file:///C:\Users\mdrahman\AppData\Local\Temp\1\msohtmlclip1\01\clip_image001.emz" o:title=""/&gt; &lt;w:wrap type="square"/&gt;&lt;/v:shape&gt;&lt;![if gte mso 9]&gt;&lt;o:OLEObject Type="Embed" ProgID="ChemDraw.Document.6.0" ShapeID="_x0000_s1027" DrawAspect="Content" ObjectID="_1475311855"&gt;&lt;/o:OLEObject&gt;&lt;![endif]&gt;&lt;![endif]--&gt;&lt;!--[if !vml]--&gt;&lt;!--[endif]--&gt; The first total synthesis of macrosalhine chloride 4 starting from D-tryptophan 1 will be presented. Key steps include an effective method to execute an enolate mediated intramolecular copper catalyzed coupling of a vinyl iodide 2 with a ketone in high yield. An unusual cyclization which is presumably formed via a radical mechanism has been inhibited with TEMPO as a radical scavenger to give only the desired cyclization product. This cyclization gives an improved route to the key intermediate 3, the pentacyclic ketone, which is common for many other C-19 methyl substituted macroline/sarpagine /ajmaline indole alkaloids. Studies on the copper–mediated mechanism and progress toward the total synthesis of the related C-19 substituted indole alkaloids macrocarpine A, B and C will be presented.

First enantiospecific total synthesis of macrosalhine chloride (4) and progress toward the synthesis of macroline-related indole alkaloids macrocarpine A, B, and C will be presented

249th National Meeting (2015)

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