Stereoselective total synthesis of oplopandiol,oploxyne A,and oploxyne B

A stereoselective total synthesis of oplopandiol, oploxyne A, and (−)-oploxyne B is described. The key reactions include Sharpless asymmetric epoxidation, d-proline catalyzed aminoxylation, Cadiot–Chodkiewicz cross-coupling reaction, m-CPBA induced substrate-controlled stereoselective epoxidation, and Lewis acid catalyzed stereo- and regioselective ring-opening of epoxide.     

Stereoselective synthesis of marine sesterterpenes, 16-deacetoxy-scalarafuran, (+)-scalarolide and their analogs

The stereoselective synthesis of C12 oxygenated marine scalaranic sesterterpenes 16-deacetoxy-scalarafuran, (+)-scalarolide and their unnatural analogs were described. Three key transformations were involved in their synthesis, which are the ring-opening rearrangement of epoxide, stereoselective Diels-Alder addition, and one-pot γ-butenolide formation process, and the absolute configurations of natural (+)-scalarolide and 16-deacetoxy-scalarafuran were confirmed.     

Total Synthesis of Notoamides F,I, and R and Sclerotiamide

The total synthesis of the natural indole alkaloids (+)‐notoamide F, I, and R and (?)‐sclerotiamide is described. The four heptacyclic compounds were synthesized in 10–12 steps in a convergent and highly stereoselective manner from the readily available Seebach acetal. Key steps of the synthesis include a stereoselective oxidative aza‐Prins cyclization to construct the bicyclo[2.2.2]diazaoctane, and a cobalt‐catalyzed radical cycloisomerization to create the cyclohexenyl ring.     

Total Synthesis of Notoamides F,I, and R and Sclerotiamide

The total synthesis of the natural indole alkaloids (+)‐notoamide F, I, and R and (−)‐sclerotiamide is described. The four heptacyclic compounds were synthesized in 10–12 steps in a convergent and highly stereoselective manner from the readily available Seebach acetal. Key steps of the synthesis include a stereoselective oxidative aza‐Prins cyclization to construct the bicyclo[2.2.2]diazaoctane, and a cobalt‐catalyzed radical cycloisomerization to create the cyclohexenyl ring.     

Short and stereoselective synthesis of manzacidins A and C, and their enantiomers

A short and stereoselective synthesis of manzacidins A and C, and their enantiomers was achieved via stereoselective hydrogenation reactions of dehydroamino acid esters 5-8 using a chiral Rh catalyst.     

Highly stereoselective synthesis of antitumor agents: both enantiomers of goniothales diol,altholactone, and isoaltholactone

A flexible stereoselective route to synthesize both enantiomers of the highly functionalized substituted tetrahydrofurans and α,β-unsaturated-δ-lactones, goniothales diol, altholactone, and isoaltholactone, from readily available cinnamyl alcohol is described. This approach derived its asymmetry from Sharpless catalytic asymmetric epoxidation and Sharpless asymmetric dihydroxylation reactions. The resulting diols were produced in high enantiomeric excess and were cyclized in a stereoselective manner in the presence of a catalytic amount of camphor sulfonic acid.     

The Stereoselective Synthesis of Disubstituted E,Z-Diene Ester

The new method for the stereoselective synthesis of disubstituted diene ester was successfully applied to a highly stereoselective synthesis of E, Z-diene ester (1).     

Stereoselective synthesis of an advanced seco ester intermediate as a precursor toward the synthesis of amphidinolides T1, T3, and T4

An efficient, convergent, and stereoselective synthesis of a very advanced intermediate toward the total synthesis of amphidinolides T1, T3, and T4 utilising Evan’s aldol and alkylation reactions, oxy-Michael, cross metathesis, stereoselective Grignard addition, and Yamaguchi esterification reactions as key steps is described.     

Cycloaddition between electron-deficient pi-systems, photochemical and radical-induced reactions: a novel, general, and stereoselective route to polyfunctionalized bridged bicyclo[2.2.2]octanes, bicyclo[3.3.0]octanes, bicyclo[4.2.0]octanes, and tricyclo[4.3.1.0(3,7)]decanes

A novel, general, and stereoselective route to functionalized bridged bicyclo[2.2.2]octanes, bicyclo[3.3.0]octanes, bicyclo[4.2.0]octanes, and tricyclo[4.3.1.0(3,7)]decanes has been described. Various functionalized and substituted bicyclo[2.2.2]octanes endowed with a beta,gamma-enone chromophore were synthesized via cycloaddition of in situ generated cyclohexa-2,4-dienones with electron-deficient 2pi partners and manipulation of the resulting adducts. Triplet sensitized irradiation of bridged bicyclooctenones led to synthesis of bicyclo[3.3.0]octanoids, whereas the direct irradiation furnished bicyclo[4.2.0]octanes in stereoselective fashion as a result of modulation of reactivity in excited states. Further, manipulation of the adducts led to appropriately appended and functionalized bicyclo[2.2.2]octanes that upon radical induced cyclization provided an efficient and stereoselective route to the tricyclo[4.3.1.0(3,7)]decane (isotwistane) framework of pupukeananes.     

The first total synthesis of (+/-)-arisugacin A, a potent, orally bioavailable inhibitor of acetylcholinesterase

The first convergent total synthesis of (+/-)-arisugacin A was accomplished by stereoselective construction of the arisugacin skeleton via a Knoevenagel-type reaction of an alpha,beta-unsaturated aldehyde with a 4-hydroxy 2-pyrone and stereoselective dihydroxylation followed by deoxygenation.     

Stereoselective total syntheses of three Lycopodium alkaloids, (-)-magellanine, (+)-magellaninone, and (+)-paniculatine, based on two Pauson-Khand reactions

The total syntheses of (-)-magellanine, (+)-magellaninone, and (+)-paniculatine were completed from diethyl l-tartrate via the common intermediate in a stereoselective manner. The crucial steps in these syntheses involved two intramolecular Pauson-Khand reactions of enynes: the first Pauson-Khand reaction constructed the bicyclo[4.3.0] carbon framework, the corresponding A and B rings of these alkaloids in a highly stereoselective manner, whereas the second Pauson-Khand reaction stereoselectively produced the bicyclo[3.3.0]skeleton, which could be converted into the C and D rings of the target natural products.     

Stereoselective preparation of dienol phosphates from alpha,beta-ethylenic aldehydes

The first stereoselective method of preparation of (E)-dienol phosphates from alpha,beta-ethylenic aldehydes is described. The key point is the stereoselective enolization of conjugated alkenals by potassium tert-butoxide in the presence of N-methylpyrrolidinone (NMP).     

Reactions between Grignard reagents and heterocyclic N-oxides: stereoselective synthesis of substituted pyridines, piperidines, and piperazines

In this perspective we discuss the recent developments of stereoselective synthesis of substituted pyridines, piperidines, and piperazines from cheap and commercially readily available starting materials. Pyridine N-oxides and pyrazine N-oxides are reacted with alkyl, aryl, alkynyl and vinyl Grignard reagents to give a diverse set of heterocycles in high yields. Optically active substituted piperazines are obtained by an asymmetric reaction from pyrazine N-oxides using sparteine as chiral ligand. In addition, a stereoselective synthesis of dienal-oximes from the reaction between pyridine N-oxides and Grignard reagents is presented, which results in a useful intermediate for the synthesis of a diverse set of compounds.     

Stereoselective synthesis of (−)-malyngolide, (+)-malyngolide and (+)-tanikolide using ring-closing metathesis

The stereoselective syntheses of the naturally occurring δ-lactones (+)-tanikolide and (−)-malyngolide as well as of the unnatural (+)-enantiomer of the latter are described. Key steps in each of these syntheses were stereoselective additions of organometallic reagents to α-oxygenated ketones and olefin ring-closing metatheses.     

Efficient and selective synthesis of D-arabino-, D-lyxo-, and D-xylo-phytosphingosine from D-ribo-phytosphingosine

A new high-yield approach to the regio- and stereoselective synthesis of d-arabino-, D-lyxo-, and D-xylo-phytosphingosines from inexpensive D-ribo-phytosphingosine is described. The synthetic methodologies mainly rely on the selective configurational inversion of the stereocenter through a neighboring group participation mechanism.     

A Flexible Approach to Grandisine Alkaloids: Total Synthesis of Grandisines B,D, and F

This article describes in detail the first total synthesis of grandisine alkaloids, grandisines B, D, and F, which show affinity for the human δ‐opioid receptor. The key steps in this synthesis are construction of the isoquinuclidinone moiety of 2 by intramolecular imine formation and the tetracyclic ring system of 4 by stereoselective ring closure of the enolate of amine 8 generated by 1,4‐addition of ammonia to 9 . Synthesis of key intermediate 9 featured a highly stereoselective Brønsted acid mediated Morita–Baylis–Hillman (MBH) reaction via the N‐acyl iminium ion.     

Stereoselective total synthesis of arenastatin A, a spongean cytotoxic depsipeptide

A highly stereoselective total synthesis of arenastatin A, an extremely potent cytotoxic cyclic depsipeptide from marine sponge, was developed. The desired 7,8-β-epoxide in arenastatin A was constructed by asymmetric sulfur ylide-mediated epoxidation in good yield and highly stereoselective manner.     

Oxidative Prins-pinacol tandem process mediated by a hypervalent iodine reagent: scope, limitations, and applications

An oxidative Prins-pinacol tandem process mediated by a hypervalent iodine reagent has been developed. This oxidative version of the famous tandem process fits within the concept of "aromatic ring umpolung" and allows the stereoselective transformation of simple phenols into highly elaborated spirocyclic dienone cores containing several quaternary carbon centers. The scope and the limitations of this process, including the study of its stereoselectivity, are described in this article. As a direct application of this stereoselective process, we describe the formal synthesis of (-)-platensimycin, an important antibiotic agent.     

Heck arylation of styrenes with arenediazonium salts: short, efficient, and stereoselective synthesis of resveratrol, DMU-212, and analogues

Short, efficient, and stereoselective synthesis of the trans-stilbenes resveratrol, DMU-212, and analogues of both compounds are described. The synthesis of these important anti-cancer agents feature the palladium catalyzed Heck-Matsuda arylation of styrenes with arenediazonium tetrafluoroborates.     

Stereocontrolled synthesis of 8,11-dideoxytetrodotoxin,unnatural analogue of puffer fish toxin

[structure: see text] 8,11-Dideoxytetrodotoxin, an unnatural tetrodotoxin analogue, was synthesized in a highly stereoselective manner from a common intermediate in our synthetic studies on tetrodotoxin. The synthesis features neighboring group participation of trichloroacetamide for stereoselective hydroxylation, protection of ortho ester, and guanidine installation with Boc-protected isothiourea.