Intramolecular carbenoid insertion : reactions of [alpha] -diazoketones derived from benzothienyl, pyrolyl and indolyl alkanoic acids with rhodium (II) acetate

Recent studies have shown that the rhodium (II) acetate decomposition chemistry observed for a-diazoketones tethered to thienyl, furanyl, and benzofuranyl moieties is dependent not only on the nature of the heteroatom but also on the length of the aliphatic tether linking the diazoketone moiety with the aromatic fragment. The present thesis expands on these results and focuses on a-diazoketones tethered to benzothiophenes, pyrroles and indoles by a methylene linker. In the case of benzothiophenes, it was shown that the rhodium catalyst decomposition of I-diazo-4-(3-benzothienyl)-2-butanone (146) and 1-diazo-4-(3benzothienyl)- 2-butanone (152) allow for the isolation of 1,2,3a,3b-tetrahydro-3Hbenzo[ b]cyclopenta[1,3]cyclopropa- [1 ,2-d]thiophen-3-one (147) and 1,2,3a,3btetrahydro- 3H-benzo[b]cyclopenta[1,3]cyclopropa[1,2-d]thiophen-3-one (153). However treatment of 1-diazo-3-(3-Benzothienyl)-2-Propanone (165) with Rh(II) acetate results in the formation of 2,3-Dihydro-1H-benzo[b]cyclopenta[d]thiophen-2-one (159), while 1diazo- 3-(2-Benzothienyl)-2-Propanone with the same condition gives 5,5-bis( 1benzothiophen- 2-ylmethyl)-2(5H)-furanone (166) along with the tricycle 159. The chemistry of the pyrrolyl and the indolyl moieties linked to terminal adiazoketone systems was also investigated. The decomposition of I-diazo-(2-pyrrolyl)-2propanone (173) results in the formation of two products; the N-H insertion product IHpyrrolizin- 2(3H)-one (176) and the alkylation product 4,6-dihydrocyclopenta[b]pyrrol5( 1 H)-one (180). When 1-Diazo-3-(3-indoly)-3-propanone (194) is treated with catalytic amount of Rh (II) 3,4-dihydrocyclopenta[b]indol-2(1H)-one (193) is isolated quantitatively. The later reaction when monitored using IH NMR the intermediate 200 can be seen whose structure was confirmed by the comparison to series of model compounds. The mechanisms underlying these reactions as well as their synthetic utility is discussed.

The Weekly Register September 1811 to March 1812

The Weekly Register, also known as Niles Weekly Register was a weekly periodical edited by Hezekiah Niles (1777-1839), and published in Baltimore Maryland. Volumes of Interest were published between 1811 (Vol. 1, No. 1, September 7, 1811) to 1814 (Vol. 5, No. 26, February 26, 1814). These volumes focus primarily on 19th century Politics and Government in the United States of America. Niles edited and published the Weekly Register until 1836, making it one of the most widely-circulated magazines in the United States. The popularity also made Niles into one of the most influential journalists of his day. Devoted primarily to politics, Niles' Weekly Register is considered an important source for the history of the period. The Register also recorded current economics, technology, science, medicine, geography, archaeology, the weather, and stories of human interest. PLEASE CLICK ON THE WEEKLY PERIODICALS ON THE RIGHT OF THE SCREEN (PDF FILES)TO DOWNLOAD FILES. Pages are divided as follows: 1811 September 7th pages 1-16 14th pages 17-32 21st pages 33-48 28th pages 49-72 1811 October 5th pages 73-88 12th pages 89-104 19th pages 105-120 26th pages 121-136 1811 November 2nd pages 137-152 9th pages 153-184 15th pages 185-208 23rd pages 209-224 30th pages 225-240 1811 December 7th pages 241-256 14th pages 257-280 21st pages 281-296 28th pages 299-320 1812 January 4th pages 321-336 11th pages 337-360 18th pages 361-376 25th pages 377-392 1812 February 1st pages 393-408 8th pages 409-432 15th pages 433-448 22nd pages 449-464 29th pages 465-480 PLEASE CLICK ON THE WEEKLY PERIODICALS ON THE RIGHT OF THE SCREEN (PDF FILES)TO DOWNLOAD FILES. Call Number: SPCL PER JK 1 N52

The Weekly Register - November 1811

Issues for the November 1811 Weekly Register newspaper (Baltimore, Maryland) are divided as follows: November 2nd, pages 137-152 November 9th, pages 153-184 November 15th, pages 185-208 November 23rd, pages 209-224 November 30th, pages 225-240 PLEASE CLICK ON THE WEEKLY PERIODICALS ON THE RIGHT OF THE SCREEN (PDF FILES)TO DOWNLOAD FILES. Look for other issues of the Weekly Register within this website. The Weekly Register, also known as Niles Weekly Register, was a weekly periodical edited by Hezekiah Niles (1777-1839) and published in Baltimore Maryland. Volumes of interest were published between 1811 (Vol. 1, No. 1, September 7, 1811) to 1814 (Vol. 5, No. 26, February 26, 1814). These volumes focus primarily on 19th century politics and government in the United States of America. Niles edited and published the Weekly Register until 1836, making it one of the most widely-circulated magazines in the United States. The popularity also made Niles into one of the most influential journalists of his day. Devoted primarily to politics, Niles' Weekly Register is considered an important source for the history of the period. The Register also recorded current economics, technology, science, medicine, geography, archaeology, the weather, and stories of human interest.Call Number: SPCL PER JK 1 N52

The Weekly Register - May 1813

Issues for the May 1813 Weekly Register newspaper (Baltimore, Maryland) are divided as follows: May 1st, pages 137-152 May 8th, pages 153-168 May 15th, pages 169-184 May 22nd, pages 185-200 May 29th, pages 201-216 PLEASE CLICK ON THE WEEKLY PERIODICALS ON THE RIGHT OF THE SCREEN (PDF FILES)TO DOWNLOAD FILES. Look for other issues of the Weekly Register within this website. The Weekly Register, also known as Niles Weekly Register, was a weekly periodical edited by Hezekiah Niles (1777-1839) and published in Baltimore Maryland. Volumes of interest were published between 1811 (Vol. 1, No. 1, September 7, 1811) to 1814 (Vol. 5, No. 26, February 26, 1814). These volumes focus primarily on 19th century politics and government in the United States of America. Niles edited and published the Weekly Register until 1836, making it one of the most widely-circulated magazines in the United States. The popularity also made Niles into one of the most influential journalists of his day. Devoted primarily to politics, Niles' Weekly Register is considered an important source for the history of the period. The Register also recorded current economics, technology, science, medicine, geography, archaeology, the weather, and stories of human interest. Call Number: SPCL PER JK 1 N52

The Weekly Register Vol. VI, No. 22, Whole No. 152- July 30, 1814

The Weekly Register, also known as Niles Weekly Register, was a weekly periodical edited by Hezekiah Niles (1777-1839) and published in Baltimore Maryland. Volumes of interest were published between 1811 (Vol. 1, No. 1, September 7, 1811) to 1814 (Vol. 5, No. 26, February 26, 1814). These volumes focus primarily on 19th century politics and government in the United States of America. Niles edited and published the Weekly Register until 1836, making it one of the most widely-circulated magazines in the United States. The popularity also made Niles into one of the most influential journalists of his day. Devoted primarily to politics, Niles' Weekly Register is considered an important source for the history of the period. The Register also recorded current economics, technology, science, medicine, geography, archaeology, the weather, and stories of human interest. This issue is part of a bound book titled the Weekly Register 1812-1814. Pages are divided as follows: November 14, 1812- Pages 161-174 January 22, 1814- Pages 337-352 July 30, 1814- Pages 361-376 Look for other issues of the Weekly Register within the website.