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1.
Org Lett ; 23(8): 2863-2867, 2021 04 16.
Article in English | MEDLINE | ID: mdl-33792325

ABSTRACT

The Pt-catalyzed diboration of cyclic alkenes is extended to unsaturated heterocycles and bicyclic compounds and can be accomplished in a diastereoselective fashion. The optimal procedures, substrate scope, and diastereoselectivity were investigated, and examples employing both homogeneous and heterogeneous catalysis were examined. Lastly, application to the construction of the nucleoside analog (±)-aristeromycin was conducted.

2.
Org Lett ; 23(9): 3379-3383, 2021 05 07.
Article in English | MEDLINE | ID: mdl-33852313

ABSTRACT

Intramolecular amination of organoboronates occurs with a 1,2-metalate shift of an aminoboron "ate" complex to form azetidines, pyrrolidines, and piperidines. Bis(boronates) undergo site-selective amination to form boronate-containing azacycles. Enantiomerically enriched azacycles are formed with high stereospecificity.

3.
J Am Chem Soc ; 138(14): 4818-23, 2016 Apr 13.
Article in English | MEDLINE | ID: mdl-27003237

ABSTRACT

We report a modular three-component dynamic kinetic resolution (DKR) that affords enantiomerically enriched hemiaminal esters derived from azoles and aldehydes. The novel and scalable reaction can be used to synthesize valuable substituted azoles in a regioselective manner by capping (e.g., acylation) of the equilibrating azole-aldehyde adduct. With the use of a prolinol-derived DMAP catalyst as the chiral Lewis base, the products can be obtained in high chemical yield and with high enantiomeric excess. The DKR was performed on a multikilogram scale to produce a tetrazole prodrug fragment for a leading clinical candidate that posed formidable synthesis challenges.


Subject(s)
Azoles/chemical synthesis , Esters/chemical synthesis , Lewis Bases/chemistry , Aldehydes/chemistry , Alkanesulfonates/chemical synthesis , Alkanesulfonates/chemistry , Azoles/chemistry , Catalysis , Esters/chemistry , Kinetics , Stereoisomerism , Tetrazoles
4.
Org Lett ; 18(3): 508-11, 2016 Feb 05.
Article in English | MEDLINE | ID: mdl-26771228

ABSTRACT

The first described reaction between N-tosylhydrazone and SO2 is reported to provide alkyl sulfonamides in the presence of various amines. In this procedurally simple method, hydrazones of both unsaturated aldehydes and ketones proceed in moderate to excellent yields. Primary and secondary aliphatic amines are accommodated in this reaction, which provides a novel route to sulfonamides.


Subject(s)
Hydrazones/chemistry , Sulfonamides/chemical synthesis , Aldehydes/chemistry , Amines/chemistry , Catalysis , Ketones/chemistry , Molecular Structure , Sulfonamides/chemistry , Sulfur Dioxide/chemistry
5.
Nat Prod Rep ; 31(4): 504-13, 2014 Apr.
Article in English | MEDLINE | ID: mdl-24514754

ABSTRACT

Despite the longstanding importance of polyketide natural products in human medicine, nearly all commercial polyketide-based drugs are prepared through fermentation or semi-synthesis. The paucity of manufacturing routes involving de novo chemical synthesis reflects the inability of current methods to concisely address the preparation of these complex structures. Direct alcohol C-H bond functionalization via"C-C bond forming transfer hydrogenation" provides a powerful, new means of constructing type I polyketides that bypasses stoichiometric use of chiral auxiliaries, premetallated C-nucleophiles, and discrete alcohol-to-aldehyde redox reactions. Using this emergent technology, total syntheses of 6-deoxyerythronolide B, bryostatin 7, trienomycins A and F, cyanolide A, roxaticin, and formal syntheses of rifamycin S and scytophycin C, were accomplished. These syntheses represent the most concise routes reported to any member of the respective natural product families.


Subject(s)
Biological Products/chemical synthesis , Polyketides/chemical synthesis , Biological Products/chemistry , Bridged Bicyclo Compounds, Heterocyclic/chemical synthesis , Bridged Bicyclo Compounds, Heterocyclic/chemistry , Bryostatins/chemical synthesis , Bryostatins/chemistry , Catalysis , Erythromycin/analogs & derivatives , Erythromycin/chemical synthesis , Erythromycin/chemistry , Humans , Hydrogenation , Macrolides/chemical synthesis , Macrolides/chemistry , Molecular Structure , Polyketides/chemistry , Rifamycins/chemical synthesis , Rifamycins/chemistry , Stereoisomerism
6.
Chem Commun (Camb) ; 49(54): 6096-8, 2013 Jul 11.
Article in English | MEDLINE | ID: mdl-23722271

ABSTRACT

The ruthenium catalyst derived from Ru3(CO)12 and triphos [Ph2P(CH2CH2PPh2)2] promotes the direct C-C coupling of isoprene with aryl substituted hydantoins 1a­1f at the diene C4-position to furnish products of n-prenylation 2a­2f. A mechanism involving hydantoin dehydrogenation followed by diene-imine oxidative coupling to furnish a transient aza-ruthencyclopentene is proposed.


Subject(s)
Butadienes/chemistry , Hemiterpenes/chemistry , Hydantoins/chemistry , Pentanes/chemistry , Ruthenium/chemistry , Alkylation , Catalysis , Coordination Complexes/chemistry , Hydrogenation , Prenylation
8.
Org Lett ; 14(24): 6302-5, 2012 Dec 21.
Article in English | MEDLINE | ID: mdl-23231774

ABSTRACT

The cyclometalated π-allyliridium 3,4-dinitro-C,O-benzoate complex modified by (R)- or (S)-Cl,MeO-BIPHEP promotes the transfer hydrogenative coupling of allyl acetate to ß-stereogenic alcohols with good to excellent levels of catalyst-directed diastereoselectivity to furnish homoallylic alcohols. Remote electronic effects of the C,O-benzoate of the catalyst play a critical role in suppressing epimerization of the transient α-stereogenic aldehyde.


Subject(s)
Alcohols/chemistry , Aldehydes/chemistry , Iridium/chemistry , Alcohols/chemical synthesis , Catalysis , Molecular Structure , Stereoisomerism
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