Attempted Synthesis of a Photoreactive Geranylcysteine Derivative.

<p>In an attempt to synthesize a photoreactive geranylcysteine derivative, <b>A</b>, with an appropriate photoprobe to be studied as a mimic for farnesylated protein, <b>B</b>, the following syntheses were carried out. The hydroxyl group of geraniol was protected with DHP/PPTs to generate <b>1</b> (98.1%). Allylic oxidation of <b>1</b> by using TBHP/SeO2 yielded <b>2</b> (31.5%). A modified oxidation increased the yield of <b>2</b> (34.4%). Treatment of <b>2</b> with BTC/pyridine afforded <b>3</b> (86.0%). Reaction of <b>3</b> with NaN3/DMF gave <b>8</b> and <b>9</b> (49.4%). Deprotection of this mixture under PPTs/EtOH afforded <b>10</b> and <b>11</b> (64.1%). Because of the unexpected reaction of <b>3</b> with N₃^-, we focused on alternative target molecules <b>12</b> and <b>13</b> (Figure 7). Our attempts to synthesize the first intermediates <b>14</b> and <b>15</b> in the syntheses of <b>12</b> and <b>13</b> (Scheme 14 and Scheme 15) have resulted in the isolation of the unreacted starting material.</p>

Name thesis:degree_name

MS (Master of Science)

Level thesis:degree_level

Thesis - restricted

Discipline thesis:degree_discipline

Chemistry

Year dc:date.issued

2004

Author dc:creator

• Li, Qian

• geranylcysteine
• photoaffinity labeling
• protein prenylation
• Chemistry
• Physical Sciences and Mathematics

Statement dc:rights

• Copyright by the authors.

Repository record dc:identifier

https://dc.etsu.edu/etd/915

OAI identifier oai:identifier

oai:dc.etsu.edu:etd-2072