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1.
J Org Chem ; 78(19): 9921-8, 2013 Oct 04.
Article in English | MEDLINE | ID: mdl-24024913

ABSTRACT

N-Prolinylanthranilamide-based pseudopeptide organocatalyst 14 was shown to promote enantioselective direct aldol reaction of 7-iodoisatin and 2,2-dimethyl-1,3-dioxan-5-one with 90% conversion (75% isolated yield), 90% enantioselectivity, and 23:1 diastereoselectivity. To demonstrate the synthetic utility of this chemistry, the racemic aldol reaction product was converted in five steps to a potential intermediate for construction of the natural product TMC-95A.

2.
J Org Chem ; 77(19): 8835-9, 2012 Oct 05.
Article in English | MEDLINE | ID: mdl-22950891

ABSTRACT

A stereocontrolled intramolecular iron-mediated diene/olefin cyclocoupling reaction has been explored using vinyl ethers as the olefin partners. Spirolactams with functionalized (alkoxymethyl) side chains can be formed under thermal conditions. With a methoxy substituent on the diene, demetalation and hydrolysis of the cyclocoupling product afforded a single diastereomer.

3.
Org Lett ; 13(20): 5548-51, 2011 Oct 21.
Article in English | MEDLINE | ID: mdl-21958056

ABSTRACT

Proline anthranilamide-based pseudopeptides were shown to be effective organocatalysts for enantioselective direct aldol reactions of a selection of aldehydes with various ketones with excellent yield, enantioselectivity up to 99% and anti to syn diastereoselectivity up to 25:1.


Subject(s)
Aldehydes/chemistry , Ketones/chemistry , ortho-Aminobenzoates/chemistry , Catalysis , Combinatorial Chemistry Techniques , Molecular Structure , Peptides/chemistry , Proline/analogs & derivatives , Proline/chemistry , Stereoisomerism
4.
J Org Chem ; 74(11): 4242-5, 2009 Jun 05.
Article in English | MEDLINE | ID: mdl-19422257

ABSTRACT

Diels-Alder reactions of cyclopentadienones, to afford substituted biaryls, were studied using an expanded substrate base. Electron-withdrawing groups on the aryl alkyne dienophile facilitated the reaction, and these substrates gave better yields than those with electron-donating substituents. Steric effects were also found to be important, and o,o'-dimethylphenylacetylene gave much poorer yield of biaryl product.


Subject(s)
Alkynes/chemistry , Bridged Bicyclo Compounds/chemical synthesis , Cyclopentanes/chemistry , Polycyclic Aromatic Hydrocarbons/chemical synthesis
5.
Tetrahedron Lett ; 49(12): 1922-1926, 2008 Mar 17.
Article in English | MEDLINE | ID: mdl-18496593

ABSTRACT

Ruthenium-mediated S(N)Ar reactions are used to construct the diaryl ether linkages in two key intermediates for a projected total synthesis of the aglycone of ristocetin A.

6.
Acta Crystallogr C ; 64(Pt 4): m147-8, 2008 Apr.
Article in English | MEDLINE | ID: mdl-18391373

ABSTRACT

The tricarbonylchromium unit bound to the arene ring of the chiral title complex, [Cr(C(19)H(26)O(3))(CO)(3)], is rotated by ca 25 degrees in agreement with the proposed mechanism for 1,5-asymmetric induction of nucleophilic attack.


Subject(s)
Bridged Bicyclo Compounds/chemistry , Chromium Compounds/chemistry , Crystallography, X-Ray , Models, Molecular , Molecular Structure
7.
J Org Chem ; 73(2): 760-3, 2008 Jan 18.
Article in English | MEDLINE | ID: mdl-18154355

ABSTRACT

A tripeptido--arene--ruthenium complex was prepared as a key precursor for the projected synthesis of orienticin C, demonstrating that the cyclopentadienylruthenium moiety can be attached to a chloroarene in the presence of multiple functionality. The ruthenium-mediated intramolecular SNAr reaction for formation of the required diaryl ether linkage was successfully tested on a model system.


Subject(s)
Macrocyclic Compounds/chemical synthesis , Models, Molecular , Organometallic Compounds/chemistry , Ruthenium/chemistry , Vancomycin/analogs & derivatives , Calixarenes/chemistry , Cyclization , Macrocyclic Compounds/chemistry , Molecular Conformation , Oligopeptides/chemistry , Stereoisomerism , Vancomycin/chemical synthesis , Vancomycin/chemistry
8.
J Org Chem ; 72(20): 7693-700, 2007 Sep 28.
Article in English | MEDLINE | ID: mdl-17824648

ABSTRACT

A stereospecific intramolecular iron tricarbonyl-promoted aldehyde-diene cyclocoupling reaction was investigated by using simple substrates 6 and more complicated substrates 30a/30b. Demetalation of the initial products converts all complexed dienes to their pure organic counterparts. In addition, the nickel-catalyzed carbonyl-ene reaction and the Prins reaction were investigated with two different substrates.

9.
J Org Chem ; 72(7): 2547-57, 2007 Mar 30.
Article in English | MEDLINE | ID: mdl-17328576

ABSTRACT

Dynamic diastereoselectivity during Fe(CO)3 promoted [6+2] ene spirocyclization of 35a and 35b, having a chiral center on the pendent side chain, was investigated and gave rise to products 28a and 28b instead of four possible isomers. From this reaction, two chiral centers are generated, with absolute stereochemistry determined by the double bond geometry and the chiral center already present. 28a/b and the diene product from demetallation of 28a are proposed as potential intermediates for total synthesis of 18-deoxycytochalasin H. Furthermore, a stepwise second cyclization and a tandem double cyclization mediated by the Fe(CO)3 moiety was investigated.

10.
Org Lett ; 8(15): 3267-9, 2006 Jul 20.
Article in English | MEDLINE | ID: mdl-16836382

ABSTRACT

[Structure: see text] The conjugate additions of different carbon nucleophiles to cyclopentadienone substrates (1 and 2) with one free hydroxyl functional group were investigated to determine the role of the hydroxyl group in controlling regiochemistry. During this reaction an unexpected intramolecular displacement of OTBS by the enolate intermediate occurs, to afford cyclopropane derivatives.

11.
J Org Chem ; 69(25): 8975-8, 2004 Dec 10.
Article in English | MEDLINE | ID: mdl-15575788

ABSTRACT

A new example is provided of completely diastereoselective polycyclization, affording the octahydrophenanthrene framework. Generation of an iron tricarbonyl stabilized pentadienyl carbocation is the triggering event of the cascade reaction. The carbocation is generated by anchimerically assisted regiospecific protonation of a double bond adjacent to the iron tricarbonyl diene moiety. Tetrafluoroboric acid ether complex appears to be the optimum reagent, affording good yields, even under catalytic conditions.

12.
Org Lett ; 6(15): 2535-8, 2004 Jul 22.
Article in English | MEDLINE | ID: mdl-15255684

ABSTRACT

[reaction: see text] A short and convenient diastereoselective synthesis of all-carbon spirocylic molecules was developed. A straightforward protocol that involves rearrangement of the diene-Fe(CO)(3) complex followed by cyclization delivers the desired product. The reaction substrates were easily prepared by reaction of an appropriate nucleophile and a cyclohexadienyl-Fe(CO)(3) cation.


Subject(s)
Alkenes/chemistry , Iron/chemistry , Spiro Compounds/chemical synthesis , Catalysis , Cyclization , Diterpenes/chemistry , Polycyclic Sesquiterpenes , Stereoisomerism , Terpenes/chemistry
13.
Org Lett ; 6(13): 2121-4, 2004 Jun 24.
Article in English | MEDLINE | ID: mdl-15200300

ABSTRACT

[reaction: see text] Vicinal stereocontrol during nucleophilic addition of tert-butyl lithiopropionate to eta(6)-anisole chromium tricarbonyl complexes with differing para substituents has been studied. Excellent vicinal double stereoinduction (>99:1) was observed when the para substituent was Si(CH(3))(3), and this has been applied to a stereoselective formal synthesis of (+/-)-erythro Juvabione. Asymmetric synthesis by chiral auxiliary directed nucleophilic addition is also discussed.


Subject(s)
Chromium/chemistry , Cyclohexanes/chemical synthesis , Organometallic Compounds/chemistry , Hempa , Organometallic Compounds/chemical synthesis , Stereoisomerism
14.
J Am Chem Soc ; 125(44): 13326-7, 2003 Nov 05.
Article in English | MEDLINE | ID: mdl-14583006

ABSTRACT

A convenient one-pot procedure to prepare angularly substituted bicyclic and tricyclic molecules with excellent diastereoselectivity in good yield was developed, by Fe(CO)5 promoted cyclization. Three transformations (complexation, isomerization, and cyclization) were realized in a single operation. The product of this reaction may be a precursor for synthesis of the alkaloid gelsemine.


Subject(s)
Alkaloids/chemical synthesis , Alkenes/chemistry , Bridged Bicyclo Compounds/chemical synthesis , Cyclization , Stereoisomerism
15.
Org Lett ; 5(14): 2457-9, 2003 Jul 10.
Article in English | MEDLINE | ID: mdl-12841754

ABSTRACT

[reaction: see text] Reactions of cyclopentadienones 1 with alkylmagnesium bromides were investigated and gave 1,4 adduct and/or 1,2 adduct.

16.
J Org Chem ; 68(13): 5361-8, 2003 Jun 27.
Article in English | MEDLINE | ID: mdl-12816500

ABSTRACT

Fluorescent photoinduced electron-transfer sensors were made from p-phenylenediamine-substituted azacrown ethers attached with a dansyl group, in which the p-phenylenediamine moiety serves as electron donor and the dansyl group acts as the acceptor. Chelation-enhanced fluorescence was observed upon addition of metal salts. Selective fluorescence response was observed for Mg(2+) and/or Ca(2+) versus Na(+) and K(+) due to size match and charge density sensitivity of the p-phenylenediamine moiety.

17.
J Org Chem ; 68(13): 5369-76, 2003 Jun 27.
Article in English | MEDLINE | ID: mdl-12816501

ABSTRACT

N-Aryl-N'-(9-methylanthryl)diaza-18-crown-6 derivatives perform as fluorescent photoinduced electron-transfer (PET) sensors with very selective response toward Ca(2+) versus Mg(2+), Na(+), and K(+). The fluorescence intensity was increased by a factor of up to 170 in the presence of Ca(ClO(4))(2). (1)H NMR studies show that metal cations affect these molecules very differently: Ca(2+) has a global effect on each molecule, while Mg(2+) affects part of each molecule, and K(+) and Na(+) affect each molecule moderately, which is very consistent with the fluorescence response.

18.
J Org Chem ; 68(6): 2161-6, 2003 Mar 21.
Article in English | MEDLINE | ID: mdl-12636375

ABSTRACT

m- or p-phenylenediamine and m- or p-chlorophenyl-substituted azacrown ether derivatives were synthesized through sequential nucleophilic substitution of [(eta(5)-cyclopentadienyl)(eta(6)-(m- or p-dichlorobenzene))]iron hexafluorophosphate by azacrown ethers and cyclohexaamines. Monoarylation is the main reaction for diazacrown ethers. The overall yield from the starting complex is 50-96% for multiple steps.

19.
J Am Chem Soc ; 125(3): 638-9, 2003 Jan 22.
Article in English | MEDLINE | ID: mdl-12526656

ABSTRACT

Intramolecular double cyclization between a cyclohexadiene-Fe(CO)3 complex and a pendant diene yielded a tricyclic molecule containing a spirocenter, with defined relative stereochemistry of four contiguous carbon centers. The nature of the substituent on the pendant diene moiety has a significant effect on the yield: an ester group leads to lower yield. The product has a conjugated cyclohexadiene or methoxycyclohexadiene system; the latter was converted to an enone.

20.
Org Lett ; 4(23): 4069-71, 2002 Nov 14.
Article in English | MEDLINE | ID: mdl-12423088

ABSTRACT

A new example of stereospecific cationic cyclization of iron tricarbonyl diene complexes with pendant alkenes and arenes is provided. Protonation of a double bond vicinal to the iron tricarbonyl diene moiety is employed to trigger the cyclization, rather than the previously reported Lewis/protic acid dehydroxylation of diastereomeric alcohols, eliminating one step of separation and avoiding some reactivity problems previously encountered for one of the alcohol diastereoisomers. [reaction: see text]

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