Concise Diverted Total Synthesis of Amphidinolide T1 and T4 from a (12E)-Cycloalkene by Selective Functionalization of the C12-C13 Double Bond

Synlett ◽  
2011 ◽  
Vol 2011 (20) ◽  
pp. 3036-3040
Author(s):  
Wei-Min Dai ◽  
Lijie Sun ◽  
Dongdong Wu ◽  
Jinlong Wu
Keyword(s):  
Double Bond ◽  
Total Synthesis ◽  
Selective Functionalization

scholarly journals Classic highlights in porphyrin and porphyrinoid total synthesis and biosynthesis

2021 ◽  
Author(s):  
Mathias O. Senge ◽  
Natalia N. Sergeeva ◽  
Karl J. Hale
Keyword(s):  
Total Synthesis ◽  
Porphyrin Ring ◽  
Selective Functionalization ◽  
Porphyrin Synthesis

The development of porphyrin synthesis is illustrated, using classic and modern-day examples, which attempt to provide insights, including mechanistic ones, into the most used methods for porphyrin ring-construction and selective functionalization.

scholarly journals Stereoselective total syntheses of (±)-sinularene and (±)-5-epi-sinularene: a general intramolecular Diels–Alder approach to tricyclic sesquiterpenes

1985 ◽  
Vol 63 (4) ◽  
pp. 993-995 ◽  
Author(s):  
Kazimierz Antczak ◽  
John F. Kingston ◽  
Alex G. Fallis
Keyword(s):  
Double Bond ◽  
Methyl Ester ◽  
Total Synthesis ◽  
Ring System ◽  
Diels Alder ◽  
Exocyclic Double Bond ◽  
Total Syntheses ◽  
Methyl Group ◽  
Secondary Hydroxyl ◽  
Selective Hydrogenolysis

Stereoselective total synthesis of (±)-sinularene and (±)-5-epi-sinularene are described. The sequence employs a "blocked" cyclopentadiene in which the cyclopropane unit also serves as a latent methyl group. Thus intramolecular [4 + 2] cycloaddition of the substituted methyl spiro[2.4]hepta-4,6-dien-1-yl)-2-pentenoate 11 affords 5-benzyloxy-6-isopropyl-8-carbomethoxytetracyclo[5.4.01,7.02,4.02,9]undec-10-ene (12) which after selective hydrogenolysis generates the tricyclo[4.4.01,6.02,8]decane (sinularene) ring system. Removal of the secondary hydroxyl function (Ph3P/CCl4/CH3CN; H2/Pd/C), reduction of the methyl ester (LiAlH4), and introduction of the exocyclic double bond (acetate pyrolysis, 550 °C) completes the synthesis of (±)-sinularene in 14 steps from cyclopentadiene. A parallel series of reactions employing the isopropyl epimer of 12 affords (±)-5-epi-sinularene.

ChemInform Abstract: Total Synthesis of Milbemycin E: Development of a Procedure for the Introduction of the 3,4-Double Bond and Synthesis of the C(1)-C(10) Fragment.

ChemInform ◽  
2010 ◽  
Vol 28 (29) ◽  
pp. no-no
Author(s):  
E. R. PARMEE ◽  
S. V. MORTLOCK ◽  
N. A. STACEY ◽  
E. J. THOMAS ◽  
O. S. MILLS
Keyword(s):  
Double Bond ◽  
Total Synthesis

Intramolecular Michael Addition of N- and O-Centred Nucleophiles to Tethered Acrylates. The Role of Double-Bond Geometry in Controlling the Diastereo- selectivity of Cyclizations Leading to 2,6-Disubstituted Tetrahydropyrans and Piperidines.

1998 ◽  
Vol 51 (1) ◽  
pp. 9 ◽  
Author(s):  
Martin G. Banwell ◽  
Brett D. Bissett ◽  
Chinh T. Bui ◽  
Ha T. T. Pham ◽  
Gregory W. Simpson
Keyword(s):  
Double Bond ◽  
Total Synthesis ◽  
Michael Addition ◽  
Reductive Amination ◽  
Major Product ◽  
Enantioselective Synthesis ◽  
Cyclization Reactions ◽  
Glandular Secretion

The oxyanion derived from hydroxyacrylate E-(5) undergoes smooth intramolecular Michael addition to give the trans-2,6-disubstituted tetrahydropyran (7) as the major product of reaction. In contrast, the oxyanion obtained from isomer Z-(5) cyclizes to give the cis-2,6-disubstituted tetrahydropyran (6) as the major product. Such chemistry has been extended to the enantioselective synthesis of (+)-(6) the acquisition of which constitutes a formal total synthesis of acid (+)-(2), a constituent of the glandular secretion from the civet cat (Viverra civetta). Reductive amination of keto acrylate (12) affords an intermediate amine which cyclizes, in situ, to give the cis-2,6-disubstituted piperidine (26). Analogous treatment of compound (13) delivers the isomeric trans-2,6-disubstituted piperidine (27) as the exclusive product of reaction. Transition state structures have been proposed to account for the diastereoselectivities observed in all of the cyclization reactions.

scholarly journals Total Synthesis of Ellagitannins via Sequential Site-Selective Functionalization of Unprotected D-Glucose

2017 ◽  
Vol 65 (1) ◽  
pp. 25-32 ◽  
Author(s):  
Hironori Takeuchi ◽  
Yoshihiro Ueda ◽  
Takumi Furuta ◽  
Takeo Kawabata
Keyword(s):  
Total Synthesis ◽  
Selective Functionalization ◽  
Site Selective

Synthetic Studies in the Veratrum Alkaloid Series. II. The Total Synthesis of Verarine, Veratramine, Jervine, and Veratrobasine

1975 ◽  
Vol 53 (12) ◽  
pp. 1796-1817 ◽  
Author(s):  
James P. Kutney ◽  
John Cable ◽  
William A. F. Gladstone ◽  
Harald W. Hanssen ◽  
G. Vijay Nair ◽  
...  
Keyword(s):  
Natural Products ◽  
Double Bond ◽  
Total Synthesis ◽  
Similar Sequence ◽  
Synthetic Studies ◽  
Subsequent Introduction ◽  
Methyl Pyridine

Coupling of 3β-acetoxy-5α-etiojerv-12(13)-en-17-one (1) with the lithio derivative of 2-ethyl-5-methylpyridine provides the crucial intermediate (3) for the subsequent elaboration to verarine. Aromatization of 3 to 4 and reduction of the latter provides a mixture from which N-acetyl-5α,6-dihydroverarine (11) was isolated. Subsequent introduction of the 5,6-double bond in the latter and removal of the N-acetate function completed the synthesis of verarine (31). In a similar sequence of reactions employing 1 and the lithio derivative of 2-ethyl-3-methoxy-5-methyl-pyridine, the resultant intermediate (54), was elaborated to 5α,6-dihydroveratramine (56). Due to known conversions of the latter to veratramine (14), jervine (32), veratrobasine (33), and 11-deoxojervine (34), the formal total synthesis of these natural products is complete.

scholarly journals Total synthesis of 7-des-O-pivaloyl-7-O-benzylbryostatin 10

2017 ◽  
Vol 15 (44) ◽  
pp. 9497-9526 ◽  
Author(s):  
Anthony P. Green ◽  
Simon Hardy ◽  
Alan T. L. Lee ◽  
Eric J. Thomas
Keyword(s):  
Double Bond ◽  
Total Synthesis

The modified Julia reaction was used to assemble the (E)-16,17-double bond in the first total synthesis of a derivative of a 20-deoxybryostatin, namely 7-des-O-pivaloyl-7-O-benzylbryostatin 10.

Total Synthesis of Amphidinolide X and Its 12Z-Isomer by Formation of the C12-C13 Trisubstituted Double Bond via Ring-Closing Metathesis

Synlett ◽  
2008 ◽  
Vol 2008 (11) ◽  
pp. 1737-1741 ◽  
Author(s):  
Wei-Min Dai ◽  
Jinlong Wu ◽  
Yile Chen ◽  
Jian Jin ◽  
Jianshu Lou ◽  
...  
Keyword(s):  
Double Bond ◽  
Total Synthesis ◽  
Ring Closing Metathesis ◽  
Trisubstituted Double Bond
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