In an attempt to synthesize a photoreactive geranylcysteine derivative, A, with an appropriate photoprobe to be studied as a mimic for farnesylated protein, B, the following syntheses were carried out. The hydroxyl group of geraniol was protected with DHP/PPTs to generate 1 (98.1%). Allylic oxidation of 1 by using TBHP/SeO2 yielded 2 (31.5%). A modified oxidation increased the yield of 2 (34.4%). Treatment of 2 with BTC/pyridine afforded 3 (86.0%). Reaction of 3 with NaN3/DMF gave 8 and 9 (49.4%). Deprotection of this mixture under PPTs/EtOH afforded 10 and 11 (64.1%). Because of the unexpected reaction of 3 with N3-, we focused on alternative target molecules 12 and 13 (Figure 7). Our attempts to synthesize the first intermediates 14 and 15 in the syntheses of 12 and 13 (Scheme 14 and Scheme 15) have resulted in the isolation of the unreacted starting material.
","abstract_html":"<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 N<sub>3</sub><sup>-</sup>, 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>","abstract_has_math":false,"creators":["Li, Qian"],"institution":null,"degree_name":"MS (Master of Science)","degree_level":"Thesis - restricted","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2004,"date_issued":"2004-08-18T07:00:00Z","date_published":"2004-08-18T07:00:00Z","updated_at":"2026-07-24T02:19:35Z","subjects":["geranylcysteine","photoaffinity labeling","protein prenylation","Chemistry","Physical Sciences and Mathematics"],"languages":[],"rights":["Copyright by the authors."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://dc.etsu.edu/etd/915","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Li, Qian"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["2004-08-18T07:00:00Z"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis - restricted"]},{"key":"thesis:degree_name","label":"Degree Name","values":["MS (Master of Science)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["geranylcysteine","photoaffinity labeling","protein prenylation","Chemistry","Physical Sciences and Mathematics"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["Copyright by the authors."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://dc.etsu.edu/context/etd/article/2072/viewcontent/LIQ072204f.pdf","https://dc.etsu.edu/etd/915"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["In an attempt to synthesize a photoreactive geranylcysteine derivative, A, with an appropriate photoprobe to be studied as a mimic for farnesylated protein, B, the following syntheses were carried out. The hydroxyl group of geraniol was protected with DHP/PPTs to generate 1 (98.1%). Allylic oxidation of 1 by using TBHP/SeO2 yielded 2 (31.5%). A modified oxidation increased the yield of 2 (34.4%). Treatment of 2 with BTC/pyridine afforded 3 (86.0%). Reaction of 3 with NaN3/DMF gave 8 and 9 (49.4%). Deprotection of this mixture under PPTs/EtOH afforded 10 and 11 (64.1%). Because of the unexpected reaction of 3 with N3-, we focused on alternative target molecules 12 and 13 (Figure 7). Our attempts to synthesize the first intermediates 14 and 15 in the syntheses of 12 and 13 (Scheme 14 and Scheme 15) have resulted in the isolation of the unreacted starting material.
"]},{"key":"dc:title","label":"Title","values":["Attempted Synthesis of a Photoreactive Geranylcysteine Derivative."]}]}],"canonical_facts":{"dc:creator":["Li, Qian"],"dc:date.issued":["2004-08-18T07:00:00Z"],"dc:description.abstract":["In an attempt to synthesize a photoreactive geranylcysteine derivative, A, with an appropriate photoprobe to be studied as a mimic for farnesylated protein, B, the following syntheses were carried out. The hydroxyl group of geraniol was protected with DHP/PPTs to generate 1 (98.1%). Allylic oxidation of 1 by using TBHP/SeO2 yielded 2 (31.5%). A modified oxidation increased the yield of 2 (34.4%). Treatment of 2 with BTC/pyridine afforded 3 (86.0%). Reaction of 3 with NaN3/DMF gave 8 and 9 (49.4%). Deprotection of this mixture under PPTs/EtOH afforded 10 and 11 (64.1%). Because of the unexpected reaction of 3 with N3-, we focused on alternative target molecules 12 and 13 (Figure 7). Our attempts to synthesize the first intermediates 14 and 15 in the syntheses of 12 and 13 (Scheme 14 and Scheme 15) have resulted in the isolation of the unreacted starting material.
"],"dc:identifier":["https://dc.etsu.edu/context/etd/article/2072/viewcontent/LIQ072204f.pdf","https://dc.etsu.edu/etd/915"],"dc:rights":["Copyright by the authors."],"dc:subject":["geranylcysteine","photoaffinity labeling","protein prenylation","Chemistry","Physical Sciences and Mathematics"],"dc:title":["Attempted Synthesis of a Photoreactive Geranylcysteine Derivative."],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis - restricted"],"thesis:degree_name":["MS (Master of Science)"]},"updated_at":"2026-07-24T02:19:35Z"}