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1.
Jiuzhou Guo Bo Li Weihao Ma Dr. Mallesham Pitchakuntla Prof. Yanxing Jia 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(35):15307-15310
A practically useful method for the formation of the highly oxygenated bicyclo[3.2.1]octane ring system through Mn(OAc)3-mediated radical cyclization of alkynyl ketones was developed, which opens up a new avenue for the total synthesis of a number of highly oxidized diterpenoids. Application of this method enabled the first total synthesis of (−)-glaucocalyxin A. Other salient features of the synthesis include a highly enantioselective conjugate addition/acylation cascade reaction, a Yamamoto aldol reaction, and an intramolecular Diels–Alder reaction to assemble the A/B ring system. 相似文献
2.
Ming Gao Ye‐Cheng Wang Kai‐Rui Yang Dr. Wei He Prof. Dr. Xiao‐Liang Yang Prof. Dr. Zhu‐Jun Yao 《Angewandte Chemie (International ed. in English)》2018,57(40):13313-13318
The first and enantioselective total synthesis of (+)‐plumisclerin A, a novel unique complex cytotoxic marine diterpenoid, has been accomplished. Around the central cyclopentane anchorage, a sequential ring‐formation protocol was adopted to generate the characteristic tricycle[4.3.1.01,5]decane and trans‐fused dihyrdopyran moiety. Scalable enantioselective LaIII‐catalyzed Michael reaction, palladium(0)‐catalyzed carbonylation and SmI2‐mediated radical conjugate addition were successfully applied in the synthesis, affording multiple grams of the complex and rigid B/C/D‐ring system having six continuous stereogenic centers and two all‐carbon quaternary centers. The trans‐fused dihyrdopyran moiety with an exo side‐chain was furnished in final stage through sequential redox transformations from a lactone precursor, which overcome the largish steric strain of the dense multiring system. The reported total synthesis also confirms the absolute chemistries of natural (+)‐plumisclerin A. 相似文献
3.
Total Synthesis of Gelsedilam by Means of a Thiol‐Mediated Diastereoselective Conjugate Addition–Aldol Reaction 下载免费PDF全文
Dr. You‐Ming Huang Dr. Yang Liu Dr. Chang‐Wu Zheng Qiao‐Wen Jin Lu Pan Ren‐Ming Pan Jun Liu Prof. Dr. Gang Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(51):18339-18342
The total synthesis of gelsedilam, which features a highly diastereoselective thiol conjugate addition–intramolecular aldol reaction to install the strained and caged [3.2.2] bridged ring system and highly efficient NiCl2/NaBH4‐mediated four‐step transformation in one‐pot to construct its five‐membered lactam ring is reported. The synthesis requires only 18 linear steps from the known compounds, providing useful strategies for the construction of the intricate ring system in the synthesis of related gelsedine‐type alkaloids. 相似文献
4.
Bo Xu Bingyang Wang Wen Xun Fayang G. Qiu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(17):5810-5813
A concise and highly stereoselective total synthesis of the Daphniphyllum alkaloids (?)‐daphenylline has been accomplished. The synthesis was started from (S)‐carvone and proceeded via a stereoselective Mg(ClO4)2‐catalyzed intramolecular amide addition cyclization, an intramolecular Diels–Alder reaction to construct the ABCD tetracyclic core architecture, and a Robinson annulation coupled with an oxidative aromatization sequence. Finally, the DF ring system was installed through an intramolecular Friedel–Crafts cyclization. The total synthesis of (?)‐daphenylline is achieved in 19 steps in the longest reaction sequence and in 7.6 % overall yield. 相似文献
5.
Catalytic Michael/Ring‐Closure Reaction of α,β‐Unsaturated Pyrazoleamides with Amidomalonates: Asymmetric Synthesis of (−)‐Paroxetine 下载免费PDF全文
Yu Zhang Yuting Liao Prof. Dr. Xiaohua Liu Qian Yao Yuhang Zhou Dr. Lili Lin Prof. Dr. Xiaoming Feng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(42):15119-15124
A highly enantioselective tandem Michael/ring‐closure reaction of α,β‐unsaturated pyrazoleamides and amidomalonates has been accomplished in the presence of a chiral N,N′‐dioxide–Yb(OTf)3 complex (Tf: trifluoromethanesulfonyl) to give various substituted chiral glutarimides with high yields and diastereo‐ and enantioselectivities. Moreover, this methodology could be used for gram‐scale manipulation and was successfully applied to the synthesis of (?)‐paroxetine. Further nonlinear and HRMS studies revealed that the real catalytically active species was a monomeric L ‐PMe2 –Yb3+ complex. A plausible transition state was proposed to explain the origin of the asymmetric induction. 相似文献
6.
Prof. Dr. Hiromichi Fujioka Kenji Nakahara Naoyuki Kotoku Yusuke Ohba Yasushi Nagatomi Tsung‐Lung Wang Yoshinari Sawama Kenichi Murai Kie Hirano Tomohiro Oki Shintaro Wakamatsu Prof. Dr. Yasuyuki Kita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(43):13861-13870
A route for the asymmetric synthesis of (?)‐stenine, a member of the Stemona alkaloid family used as folk medicine in Asian countries, is described. The key features of the sequence employed include stereoselective transformations on a cyclohexane ring controlled by a chiral auxiliary unit and an intramolecular Mitsunobu reaction to construct the perhydroindole ring system. By using an intermediate in the route to (?)‐stenine, an asymmetric synthesis of 9a‐epi‐stenine was also executed. The C(9a) stereocenter in 9a‐epi‐stenine was installed by using a Staudinger/aza‐Wittig reaction of a keto–azide precursor followed by reduction of the resulting imine. The results of this effort demonstrate the applicability of the chiral auxiliary based strategy to the preparation of naturally occurring alkaloids that contain highly functionalized cyclohexane cores. 相似文献
7.
Long Min Yang Zhang Xuefeng Liang Junrong Huang Wenli Bao Dr. Chi‐Sing Lee 《Angewandte Chemie (International ed. in English)》2014,53(42):11294-11297
A highly diastereoselective and practical biomimetic total synthesis of (±)‐basiliolide B has been achieved through the study of the two proposed biosynthetic pathways (O‐methylation and O‐acylation) for the unprecedented 7‐methoxy‐4,5‐dihydro‐3H‐oxepin‐2‐one (C ring). The synthesis featured a cyclopropanation/ring opening strategy for establishing the stereogenic centers at C8 and C9, a biomimetic 2‐pyrone Diels–Alder cycloaddition for the synthesis of the ABD ring system, and finally a highly efficient biomimetic intramolecular O‐acylation for the C ring formation. This result provides an important perspective on the biosynthetic origin of the unprecedented 7‐membered acyl ketene acetal moiety of the C ring. 相似文献
8.
Shuyu Chu Dr. Stephen Wallace Prof. Dr. Martin D. Smith 《Angewandte Chemie (International ed. in English)》2014,53(50):13826-13829
A concise and efficient synthesis of (?)‐gephyrotoxin from L ‐pyroglutaminol has been realized. The key step in this approach is a diastereoselective intramolecular enamine/Michael cascade reaction that forms two rings and two stereocenters and generates a stable tricyclic iminium cation. A hydroxy‐directed reduction of this intermediate plays a key role in establishing the required cis‐decahydroquinoline ring system, enabling the total synthesis of (?)‐gephyrotoxin in nine steps and 14 % overall yield. The absolute configuration of the synthetic material was confirmed by single‐crystal X‐ray diffraction and is consistent with the structure originally proposed for material isolated from the natural source. 相似文献
9.
Jie Ouyang Rui Yan Xianwei Mi Prof. Dr. Ran Hong 《Angewandte Chemie (International ed. in English)》2015,54(37):10940-10943
The first total synthesis of (?)‐hosieine A was accomplished and features an unprecedented nitroso–ene cyclization to construct the 2‐azabicyclo[3.2.1]octane ring system. Phosphine‐enabled stereoselective bromohydrination provided interesting mechanistic insights into the anti‐Markovnikov process. Also noteworthy is the retention of stereochemistry at C9 in the facile radical debromination initiated by Et3B/air. 相似文献
10.
Gang Liu Tian‐Jun Wu Dr. Yuan‐Ping Ruan Prof. Pei‐Qiang Huang Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(19):5755-5768
The asymmetric total synthesis of natural azasugars (+)‐castanospermine, (+)‐7‐deoxy‐6‐epi‐castanospermine, and synthetic (+)‐1‐epi‐castanospermine has been accomplished in nine to ten steps from a common chiral building block (S)‐ 8 . The method features a powerful chiral relay strategy consisting of a highly diastereoselective vinylogous Mukaiyama‐type reaction with either chiral or achiral aldehydes (≥95 % de; de=diastereomeric excess) and a diastereodivergent reduction of tetramic acids, which allows formation of three continuous stereogenic centers with high diastereoselectivities. The method also provides a flexible access to structural arrays of 5‐(α‐hydroxyalkyl)tetramic acids, such as 17/34 , and 5‐(α‐hydroxyalkyl)‐4‐hydroxyl‐2‐pyrrolidinones, such as 18 and 25/35 a . The method constitutes the first realization of the challenging chiral synthons A and D and thus of the conceptually attractive retrosynthetic analysis shown in Scheme 1 in a highly enantioselective manner. 相似文献
11.
Soonho Hwang Prof. Dr. Deukjoon Kim Prof. Dr. Sanghee Kim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(32):9977-9982
A highly stereoselective and efficient total synthesis of trans‐dihydronarciclasine from a readily available chiral starting material was developed. The synthesis defines two of the five stereogenic centers of the natural product by an amino acid ester–enolate Claisen rearrangement. The other three stereogenic centers are created in a highly stereocontrolled fashion via a six‐ring vinylogous ester intermediate, which is generated from the γ,δ‐unsaturated ester functional group of the Claisen rearrangement product in an efficient three‐step sequence. This concise total synthesis exemplifies the use of a highly regioselective Friedel–Crafts‐type cyclization to form the B ring via an isocyanate intermediate derived from an N‐Boc group, which is superior to the conventional method using an imino triflate intermediate. This same N‐Boc group is employed to give high selectivity in the Claisen rearrangement earlier in the sequence. 相似文献
12.
Prof. Dr. J. Stephen Clark Dr. Chao Xu 《Angewandte Chemie (International ed. in English)》2016,55(13):4332-4335
A highly efficient 12‐step synthesis of the marine alkaloid (?)‐nakadomarin A has been accomplished. The key advanced intermediate, a tetracyclic ketone derivative, was constructed in just seven steps using a sequence that includes an asymmetric Pauson–Khand reaction, an Overman rearrangement reaction, a ring‐closing metathesis reaction, and an amination reaction. Late introduction of the furan ring during the synthesis of (?)‐nakadomarin A means that the key tetracyclic ketone derivative has the potential to serve as an advanced intermediate for the synthesis of related marine alkaloids. 相似文献
13.
Stereoselective Total Synthesis of Hetisine‐type C20‐Diterpenoid Alkaloids: Spirasine IV and XI 下载免费PDF全文
Quanzheng Zhang Zhongshan Zhang Zhong Huang Changhui Zhang Song Xi Prof. Dr. Min Zhang 《Angewandte Chemie (International ed. in English)》2018,57(4):937-941
The first total synthesis of the architecturally complex hetisine‐type heptacyclic C20‐diterpenoid alkaloids (±)‐spirasine IV and XI is reported. The A/F/G/C tetracyclic skeleton with the challenging N?C6 and C14?C20 linkages was efficiently constructed by an intramolecular azomethine‐ylide‐based 1,3‐dipolar cycloaddition with unusual regioselectivity. SmI2‐mediated free‐radical addition to the arene moiety without prior dearomatization and a stereoselective intramolecular aldol reaction further enabled rapid access to the hetisine core, providing a bicyclo[2.2.2]octane ring with a new oxygen substitution pattern. 相似文献
14.
Dr. Didier Zurwerra M. Sc. Chem. Florian Glaus M. Sc. Chem. Leo Betschart Julia Schuster Prof. Dr. Jürg Gertsch Dr. Walter Ganci Prof. Dr. Karl‐Heinz Altmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(52):16868-16883
A new total synthesis of the marine macrolide (?)‐zampanolide ( 1 ) and the structurally and stereochemically related non‐natural levorotatory enantiomer of (+)‐dactylolide ( 2 ), that is, ent‐ 2 , has been developed. The synthesis features a high‐yielding, selective intramolecular Horner–Wadsworth–Emmons (HWE) reaction to close the 20‐membered macrolactone ring of 1 and ent‐ 2 . The β‐keto phosphonate/aldehyde precursor for the ring‐closure reaction was obtained by esterification of a ω‐diethylphosphono carboxylic acid fragment and a secondary alcohol fragment incorporating the THP ring that is embedded in the macrocyclic core structure of 1 and ent‐ 2 . THP ring formation was accomplished through a segment coupling Prins‐type cyclization. Employing the same overall strategy, 13‐desmethylene‐ent‐ 2 as well as the monocyclic desTHP derivatives of 1 and ent‐ 2 were prepared. Synthetic 1 inhibited human cancer cell growth in vitro with nM IC50 values, while ent‐ 2 , which lacks the diene‐containing hemiaminal‐linked side chain of 1 , is 25‐ to 260‐fold less active. 13‐Desmethylene‐ent‐ 2 as well as the reduced versions of ent‐ 2 and 13‐desmethylene‐ent‐ 2 all showed similar cellular activity as ent‐ 2 itself. The same activity level was attained by the monocyclic desTHP derivative of 1 . Oxidation of the aldehyde functionality of ent‐ 2 gave a carboxylic acid that was converted into the corresponding N‐hexyl amide. The latter showed only μM antiproliferative activity, thus being several hundred‐fold less potent than 1 . 相似文献
15.
Hiroaki Chiba Yuki Sakai Ayako Ohara Dr. Shinya Oishi Prof. Dr. Nobutaka Fujii Prof. Dr. Hiroaki Ohno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(27):8875-8883
The total synthesis of the pentacyclic tetrahydroisoquinoline alkaloid quinocarcin, which possesses intriguing structural and biological features, has been achieved through a gold(I)‐catalyzed regioselective hydroamination reaction. It is noteworthy that the regioselectivity of the intramolecular hydroamination of an unsymmetrical alkyne could be completely switched through substrate control. Other key features of this synthesis include the highly stereoselective synthesis of 2,5‐cis‐pyrrolidine through the intramolecular amination of the bromoallene and the Lewis acid mediated ring opening of dihydrobenzofuran. 相似文献
16.
Lian‐Dong Guo Xiong‐Zhi Huang Shi‐Peng Luo Wen‐Sen Cao Prof. Yuan‐Ping Ruan Dr. Jian‐Liang Ye Prof. Dr. Pei‐Qiang Huang 《Angewandte Chemie (International ed. in English)》2016,55(12):4064-4068
The first total synthesis of the alkaloid (?)‐haliclonin A is reported. The asymmetric synthesis relied on a novel organocatalytic asymmetric conjugate addition of nitromethane with 3‐alkenyl cyclohex‐2‐enone to set the stereochemistry of the all‐carbon quaternary stereogenic center. The synthesis also features a Pd‐promoted cyclization to form the 3‐azabicyclo[3,3,1]nonane core, a SmI2‐mediated intermolecular reductive coupling of enone with aldehyde to form the requisite secondary chiral alcohol, ring‐closing alkene and alkyne metathesis reactions to build the two aza‐macrocyclic ring systems, and an unprecedented direct transformation of enol into enone. 相似文献
17.
Zhuliang Zhong Donghui Ma Gaoyuan Zhao Huilin Li Dengyu Xu Dr. Xingang Xie Prof. Dr. Xuegong She 《化学:亚洲杂志》2015,10(12):2599-2603
The first asymmetric total synthesis of kravanhin B has been accomplished with a linear reaction sequence of 13 steps starting from (R)‐(?)‐carvone. The synthesis features an intramolecular aldol cyclization to construct the desired cis‐fused decalin skeleton and an acid‐catalyzed dehydration and olefin isomerization to install the γ‐butenolide ring. 相似文献
18.
Shuaijiang Jin Jing Gong Prof. Yong Qin 《Angewandte Chemie (International ed. in English)》2015,54(7):2228-2231
A 15‐step total synthesis of (?)‐lundurine A ( 1 ) from easily accessible (S)‐pyrrolidinone 18 is reported. A Simmons‐Smith reaction allows the efficient, simultaneous assembly of the cyclopropyl C ring, the six‐membered D ring, the seven‐membered E ring, and the quaternary carbon stereocenters at C2 and C7. The absolute configuration of natural (?)‐lundurine A was deduced to be 2R,7R,20R based on the stepwise construction of the stereocenters during the total synthesis. 相似文献
19.
Hong‐Xiu Huang Shuai‐Jiang Jin Jin Gong Dr. Dan Zhang Dr. Hao Song Prof. Yong Qin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(38):13284-13290
The bioactive Kopsia alkaloids lundurines A–D are the only natural products known to contain indolylcyclopropane. Achieving their syntheses can provide important insights into their biogenesis, as well as novel synthetic routes for complex natural products. Asymmetric total synthesis of (?)‐lundurine A has previously been achieved through a Simmons–Smith cyclopropanation strategy. Here, the total synthesis of (?)‐lundurine A was carried out using a metal‐catalyzed diazo cyclopropanation strategy. In order to avoid a carbene C?H insertion side reaction during cyclopropanation of α‐diazo‐ carboxylates or cyanides, a one‐pot, copper‐catalyzed Bamford–Stevens diazotization/diazo decomposition/cyclopropanation cascade was developed, involving hydrazone. This approach simultaneously generates the C/D/E ring system and the two chiral quaternary centers at C2 and C7. 相似文献
20.
Yonglei Que Hao Shao Haibing He Shuanhu Gao 《Angewandte Chemie (International ed. in English)》2020,59(19):7444-7449
The asymmetric total synthesis of farnesin, a rearranged ent‐kaurenoid, was achieved through a convergent approach involving photo‐Nazarov and intramolecular aldol cyclizations to build the syn‐syn‐syn hydrofluorenol ABC ring system and bicyclo[3.2.1]octane CD ring system in the first application of a UV‐light‐induced excited‐state Nazarov cyclization of a non‐aromatic dicyclic divinyl ketone in a total synthesis. Unlike the conventional acid‐promoted ground‐state Nazarov reaction, the excited‐state Nazarov reaction enables stereospecific formation of the highly strained syn‐syn‐syn‐fused hydrofluorenone scaffold through a disrotatory cyclization. 相似文献