The synthesis of a key intermediate in the total synthesis of insect antifeedant clerodanes

Published on Jan 1, 1989in Tetrahedron2.379
· DOI :10.1016/S0040-4020(01)89504-1
Jan Vader6
Estimated H-index: 6
Lucas L. Doddema1
Estimated H-index: 1
+ 3 AuthorsPaul T. Beurskens22
Estimated H-index: 22
(Radboud University Nijmegen)
The synthesis of a key intermediate, 1,2,3,4,4a,5,6,7,8,8aβ-perhydro-4α-isopropyldimethylsilyloxy-4aα-isopropyldimethylsilyloxy-methyl-1α,2α-dimethyl-5-methylene-naphthalene-1β-carbaldehyde 31 , in the total synthesis of insect antifeedant clerodanes is described. The stereochemistry of this intermediate is proven by an X-ray analysis of one of its precursors e.g. 10α-acetoxy-7β-(1,3-dioxolan-2-yl)-3,3aβ,4,5,6,6aβ,7,8,9,10-octahydro-7α,8α-dimethyl-1H-naphtho[1,8aα-c] furan 25 . Crystal data: C 19 H 30 O 5 ; monoclinic, P2 1 /n, cell dimensions: a=7.9714(4), b=11.1722(4), c=19.7783(5) A, β=92.595(5) °, Z=4; conventional R-factor=0.053.
  • References (29)
  • Citations (9)
📖 Papers frequently viewed together
1 Citations
1 Citations
78% of Scinapse members use related papers. After signing in, all features are FREE.
90 CitationsSource
#1Jan VaderH-Index: 6
#2Rimco KoopmansH-Index: 1
Last. Kerk van der S. MH-Index: 2
view all 5 authors...
Abstract New reagents for the stereoselective synthesis of 2-substituted perhydrofuro[2,3b]furanas are described. Ia the successful approach towards the latter compounds, the key steps were the addition of a aonolithio-2α-methoxy-3β-[(phenylsulfonyl)-methyilperhydrofuran to an aldehyde and a dilithio-2α-methoxy-3β-[(pheaylsulfonyl)-methyl]perhydrofuran to a carboxy1 derivative, respectively. The structures and conformations of the 2-tert-butylmtyl- and Z-isopropylper-hydrofuro [2,3b]furans were ...
14 CitationsSource
#1Takashi Tokoroyama (OCU: Osaka City University)H-Index: 18
#2K. Fujimori (OCU: Osaka City University)H-Index: 5
Last. Hideo Iio (OCU: Osaka City University)H-Index: 14
view all 6 authors...
Abstract A general method for the syntheses of cis - and trans -clerodane diterpenoids has been developed and its applications to the total syntheses of both representatives 11 and maingayic acid (32) in racemic forms are described. The common Δ 4 -3-octalone intermediates 2a and 2b were prepared from 3,4-dimethyl-2-cyclohexenone by a stereospecific conjugate addition-alkylation sequence and the subsequent thermodynamically controlled annelation. The dimethylcuprate addition to 2a followed by en...
17 CitationsSource
#1Groot de AeH-Index: 29
#2R. M. PeperzakH-Index: 6
Last. Jan VaderH-Index: 6
view all 3 authors...
Abstract The oxidative functionalization of cyclic- and bicyclic-α,β-unsaturated ketones to β-(phenylthio)-α,β-unsaturated ketones was accomplished in high yields via addition of thiophenol followed by chlorination with chloreal and spontaneous elimination of hydrochloric acid.
7 CitationsSource
#1Takashi Tokoroyama (OCU: Osaka City University)H-Index: 18
#2Masamitsu Tsukamoto (OCU: Osaka City University)H-Index: 7
Last. Hideo Iio (OCU: Osaka City University)H-Index: 14
view all 4 authors...
Doubly stereocontrolled cyclization of the allylsilane derivative 1 followed by trapping of the enolate with ClCH2SMe gives in one-pot manner the decalone derivatve 5 in which all of the four contiguous diastereomeric centers of cis-clerodane skeleton have been secured. The total synthesis of linaridial 4 have been accomplished from 5.
19 CitationsSource
Novel diterpenes, agelasine-A, -B, -C, -D, -E, and -F were isolated from the Okinawan marine sponge Agelas nakamurai Hoshino and their structures were established to be monocyclic and bicyclic diterpenes having a 9-methyladeninium unit by spectral analyses and chemical transformations.
57 CitationsSource
#1Shunichi Manabe (Mitsubishi)H-Index: 7
#2Chikao Nishino (Mitsubishi)H-Index: 16
Abstract To piscicidal solidagolactones [IV, V, VII and VIII (1~4, cis -clerodane diterpenes)] isolated from Solidago altissima , a non-steroidal conformation was assigned on the basis of chemical and physicocheaical evidence. 13 C NMR chemical shifts of methyl groups proved useful for determining stereochemistry of the A/B ring junction in clerodanes. For clerodanes having an epoxide, 1 H NMR data and the Tori equation were useful for assigning the epoxide configuration. Cremer's puckering para...
55 CitationsSource
#1Philip J. Pye (Imperial College London)H-Index: 16
#2Steven V. Ley (Imperial College London)H-Index: 74
Last. Alan J. Whittle (Imperial College London)H-Index: 6
view all 4 authors...
Abstract The first total synthesis of the diterpene clerodane insect antifeedant ajugarin I (1) has been achieved. The key step of the synthesis discloses the use of the 1,3-dithiolane unit to stereochemically direct the conjugate addition of a but-3-enyl cuprate to set in place the C-10 sp 3 carbon centre. The trans -fused ring geometry was obtained by conjugate additon of a vinyl cuprate to an enone and regio and stereoselectively trapping the resulting enolate with formaldehyde. Introduction ...
51 CitationsSource
#1Aluru Sudarsana Sharma (IACS: Indian Association for the Cultivation of Science)H-Index: 1
#2Ashok Kumar Gayen (IACS: Indian Association for the Cultivation of Science)H-Index: 2
Abstract A stereocontrolled total synthesis of the title compound, a marine natural product as well as a degradation product of sigmosceptrellins and palauolide, has been accomplished by a simple route broadly applicable to certain trans-clerodanes and congeners. In addition, the synthesis of two key degradation products of ilimaquinone, which can serve as trans-clerodane precursors, and 4,4-ethylene-dioxy-9α-(2-hydroxyethyl)-5β, 8β,9β-trimethyl-trans-decalin, an intermediate employed earlier in...
8 CitationsSource
#1Leander J. ValdesH-Index: 7
#2William M. ButlerH-Index: 26
Last. Masato KoreedaH-Index: 32
view all 5 authors...
136 CitationsSource
Cited By9
#1Peter ŠafářH-Index: 6
Last. Adam Daïch (University of Le Havre)H-Index: 16
view all 9 authors...
Abstract New homochiral 6-ethyl-7,8-indolizidinediol derivatives, related to the bioactive dihydroxylated indolizidine alkaloids, are reported to be easily accessible in four or five steps from enantiopure 9-hydroxy-octahydrofuro[3,2- f ]indolizin-6(2 H )-ones in good overall yields and high diastereomeric purities. The simple procedure used herein involves a regiospecific THF-ring opening as a key step, in addition to the C–Br linkage reduction, and the alcohol deprotection followed by lactam r...
10 CitationsSource
#1A. KrutošókováH-Index: 1
#2T. GraczaH-Index: 1
This chapter deals with 5:5 fused heterocyclic systems containing one heteroatom in each ring, where the heteroatoms may be the same or different and are O, NH, S, Se, Te, P, As and Sb. There are four possible modes of 5:5 fusion of the simple five-membered heterocycles leading to four general structures. The fully conjugated title compounds have a central C–C bond and are isoelectronic with the 10π-electron pentalene dianion. The scope of the chapter is outlined with a survey of the various str...
7 CitationsSource
#1Hans J. Reich (UW: University of Wisconsin-Madison)H-Index: 47
#2Susan WollowitzH-Index: 9
Hydrogenation and dehydrogenation reactions play a key role in synthetic organic chemistry. The discoveries that selenium and sulfur substituents could be easily introduced α to a variety of acidifying functional groups, and that these derivatives could be smoothly converted to olefins by selenoxide or sulfoxide syn elimination under mild conditions greatly broadened the range of α,β-unsaturated carbonyl compounds that could be prepared from their saturated analogs. This chapter covers the prepa...
8 CitationsSource
#1Mehmet Emin Sengul (METU: Middle East Technical University)H-Index: 1
#2Nermin Simsek (Atatürk University)H-Index: 1
Last. Metin BalciH-Index: 26
view all 3 authors...
CoII-tetraphenylporphyrin-catalyzed decomposition of bicyclic endoperoxides 4 and 5 with a strained double bond moiety has been studied. Compounds 4 and 5 have been synthesized by photooxygenation of 3 which itself was obtained by dichloroketene addition to cycloheptatriene, followed by removal of the chlorine atoms. An unusual decomposition mode of 4 promoted by CoII-TPP resulted in the formation of 8 and 9 which are important building blocks in furofuran systems.
7 CitationsSource
#2H. JongejanH-Index: 6
Last. Groot de AeH-Index: 29
view all 7 authors...
Abstract Crude lipase from Candida rugosa (CRL) is able to resolve the C3-stereoisomers of the furo[2,3b]furan building block methyl 2-methoxytetrahydrofuran-3-carboxylate 6 by alcoholysis using n -butanol in octane. The reaction is not affected by the configuration at C2. The absolute configuration of the product 7 is 3S as determined by X-ray analysis of the crystalline derivative 14 . The stereochemical outcome of the reaction is compared to the active site model derived by the group of Kazla...
21 CitationsSource
1 CitationsSource
#1Frederic Petit (CNRS: Centre national de la recherche scientifique)H-Index: 2
#2Roland Furstoss (CNRS: Centre national de la recherche scientifique)H-Index: 37
Abstract Several bicyclic [n.2.0] ketones were submitted to enzymatic Baeyer-Villiger oxidation and provided the corresponding regioisomeric lactones showing high enantiopurities. These products could be used as interesting chirons for the synthesis of various natural compounds. The absolute configurations of the obtained lactones were assigned using circular dichroism measurements.
55 CitationsSource
#1H. Bouchard (École Polytechnique)H-Index: 2
#2Josette Soulié (École Polytechnique)H-Index: 9
Last. Jean-Yves Lallemand (École Polytechnique)H-Index: 21
view all 3 authors...
Abstract A highly stereo- and enantioselective approach to clerodin 1 , an insect antifeedant, is described. The key step involved the stereospecific formation of the C 9 -C 11 bond, at an early stage of the synthesis, using a Claisen rearrangement.
8 CitationsSource
#1Jan VaderH-Index: 6
#2L. L. DoddemaH-Index: 1
Last. Paul T. BeurskensH-Index: 22
view all 6 authors...