Vladimir Birman

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Organization: Washington University

Department: Department of Chemistry

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TOPICS

Organic Chemistry

Asymmetric Synthesis Organocatalysis

Chemicals
References

Biogenetically Inspired Synthesis of Lingzhiol

Co-reporter:Krishna Sharmah Gautam and Vladimir B. Birman

Organic Letters 2016 Volume 18(Issue 7) pp:1499-1501

Publication Date(Web):March 14, 2016

DOI:10.1021/acs.orglett.5b03212

A concise stereo- and enantioselective synthesis of lingzhiol has been achieved featuring a biogenetically inspired Brønsted acid catalyzed semipinacol rearrangement of a glycidyl alcohol intermediate.

Asymmetric Catalytic Synthesis of Thiochromenes via an Acyl Transfer-Initiated Cascade

Co-reporter:Nicholas A. Ahlemeyer and Vladimir B. Birman

Organic Letters 2016 Volume 18(Issue 14) pp:3454-3457

Publication Date(Web):July 6, 2016

DOI:10.1021/acs.orglett.6b01639

A novel, reagent-free catalytic transformation of α,β-unsaturated thioesters into 2-substituted thiochromenes has been developed, with carbon dioxide as the only byproduct. Amidine-based catalysts, particularly homobenzotetramisole and its analogues, achieve high enantioselectivities and yields in this process.

Kinetic Resolution of N-Acyl-Thiolactams via Catalytic Enantioselective Deacylation

Co-reporter:Valentina D. Bumbu, Xing Yang, and Vladimir B. Birman

Organic Letters 2013 Volume 15(Issue 11) pp:2790-2793

Publication Date(Web):May 17, 2013

DOI:10.1021/ol401122g

Methanolysis of N-acyl-thiazolidin-2-thiones and -oxazolidin-2-thiones in the presence of acyl transfer catalyst benzotetramisole (BTM) proceeds in a highly enantioselective fashion thus enabling kinetic resolution of these substrates.

Catalytic, Enantioselective N-Acylation of Lactams and Thiolactams Using Amidine-Based Catalysts

Co-reporter:Xing Yang ; Valentina D. Bumbu ; Peng Liu ; Ximin Li ; Hui Jiang ; Eric W. Uffman ; Lei Guo ; Wei Zhang ; Xuntian Jiang ; K. N. Houk ;Vladimir B. Birman

Journal of the American Chemical Society 2012 Volume 134(Issue 42) pp:17605-17612

Publication Date(Web):October 2, 2012

DOI:10.1021/ja306766n

In contrast to alcohols and amines, racemic lactams and thiolactams cannot be resolved directly via enzymatic acylation or classical resolution. Asymmetric N-acylation promoted by amidine-based catalysts, particularly Cl-PIQ 2 and BTM 3, provides a convenient method for the kinetic resolution of these valuable compounds and often achieves excellent levels of enantioselectivity in this process. Density functional theory calculations indicate that the reaction occurs via N-acylation of the lactim tautomer and that cation−π interactions play a key role in the chiral recognition of lactam substrates.

Origin of Enantioselectivity in Benzotetramisole-Catalyzed Dynamic Kinetic Resolution of Azlactones

Co-reporter:Peng Liu, Xing Yang, Vladimir B. Birman, and K. N. Houk

Organic Letters 2012 Volume 14(Issue 13) pp:3288-3291

Publication Date(Web):June 11, 2012

DOI:10.1021/ol301243f

Density functional theory (DFT) calculations were performed to investigate the origins of enantioselectivity in benzotetramisole (BTM)-catalyzed dynamic kinetic resolution of azlactones. The transition states of the fast-reacting enantiomer are stabilized by electrostatic interactions between the amide carbonyl group and the acetate anion bound to the nucleophile. The chiral BTM catalyst confines the conformation of the α-carbon and the facial selectivity of the nucleophilic attack to promote such electrostatic attractions.

Kinetic Resolution of Secondary Alcohols Using Amidine-Based Catalysts

Co-reporter:Ximin Li, Hui Jiang, Eric W. Uffman, Lei Guo, Yuhua Zhang, Xing Yang, and Vladimir B. Birman

The Journal of Organic Chemistry 2012 Volume 77(Issue 4) pp:1722-1737

Publication Date(Web):January 20, 2012

DOI:10.1021/jo202220x

Kinetic resolution of racemic alcohols has been traditionally achieved via enzymatic enantioselective esterification and ester hydrolysis. However, there has long been considerable interest in devising nonenzymatic alternative methods for this transformation. Amidine-based catalysts (ABCs), a new class of enantioselective acyl transfer catalysts developed in our group, have demonstrated, inter alia, high efficacy in the kinetic resolution of benzylic, allylic, and propargylic secondary alcohols and 2-substituted cycloalkanols, and thus provide a viable alternative to enzymes.

Manifestation of FelkinAnh Control in Enantioselective Acyl Transfer Catalysis: Kinetic Resolution of Carboxylic Acids

Co-reporter:Xing Yang;Peng Liu; K. N. Houk; Vladimir B. Birman

Angewandte Chemie International Edition 2012 Volume 51( Issue 38) pp:9638-9642

Publication Date(Web):

DOI:10.1002/anie.201203327

Kinetic Resolution of N-Acyl-β-Lactams via Benzotetramisole-Catalyzed Enantioselective Alcoholysis

Co-reporter:Valentina D. Bumbu ;Vladimir B. Birman

Journal of the American Chemical Society 2011 Volume 133(Issue 35) pp:13902-13905

Publication Date(Web):August 8, 2011

DOI:10.1021/ja2058633

The first nonenzymatic kinetic resolution of β-lactams has been achieved. Alcoholysis of their N-aroyl derivatives in the presence of a simple chiral acyl transfer catalyst, benzotetramisole, produces β-amino acid derivatives with excellent enantioselectivity.

Dynamic Kinetic Resolution of Azlactones Catalyzed by Chiral Brønsted Acids

Co-reporter:Guojian Lu and Vladimir B. Birman

Organic Letters 2011 Volume 13(Issue 3) pp:356-358

Publication Date(Web):December 22, 2010

DOI:10.1021/ol102736t

Chiral Brønsted acids have been shown for the first time to catalyze the dynamic kinetic resolution of azlactones. 3,3′-Bis-(9-anthryl)-BINOL phosphoric acid 3c is particularly effective in the case of 4-aryl-substituted substrates, producing 85−92% ee’s.

Nonenzymatic Dynamic Kinetic Resolution of -(Arylthio)- and -(Alkylthio)alkanoic Acids

Co-reporter:Xing Yang ; Vladimir B. Birman

Angewandte Chemie International Edition 2011 Volume 50( Issue 24) pp:5553-5555

Publication Date(Web):

DOI:10.1002/anie.201007860

Kinetic Resolution of -Substituted Alkanoic Acids Promoted by Homobenzotetramisole

Co-reporter:Xing Yang ; Vladimir B. Birman

Chemistry - A European Journal 2011 Volume 17( Issue 40) pp:11296-11304

Publication Date(Web):

DOI:10.1002/chem.201101028

Abstract

A new method for catalytic nonenzymatic kinetic resolution of α-substituted alkanoic acids has been developed, which relies on their activation with DCC followed by enantioselective alcoholysis of the intermediate symm-anhydrides in the presence of the amidine-based catalyst homobenzotetramisole (HBTM). Moderate to excellent selectivity factors (s=5–96) have been obtained in the case of several classes of substrates, namely, α-aryl-, α-aryloxy/alkoxy-, α-halo-, α-azido-, and α-phthalimido-alkanoic acids. Under similar conditions, α-(arylthio/alkylthio)-alkanoic acids undergo dynamic kinetic resolution providing corresponding esters in up to 92 % ee and up to 93 % yield.

Nonenzymatic Dynamic Kinetic Resolution of -(Arylthio)- and -(Alkylthio)alkanoic Acids

Co-reporter:Xing Yang ; Vladimir B. Birman

Angewandte Chemie 2011 Volume 123( Issue 24) pp:5667-5669

Publication Date(Web):

DOI:10.1002/ange.201007860

Benzotetramisole-Catalyzed Dynamic Kinetic Resolution of Azlactones

Co-reporter:Xing Yang, Guojian Lu and Vladimir B. Birman

Organic Letters 2010 Volume 12(Issue 4) pp:892-895

Publication Date(Web):January 25, 2010

DOI:10.1021/ol902969j

Enantioselective acyl transfer catalyst benzotetramisole (BTM) has been found to promote dynamic kinetic resolution of azlactones providing di(1-naphthyl)methyl esters of α-amino acids with up to 96% ee.

A Cope Rearrangement-Based Route to Hexahydroazulenes

Co-reporter:Curtis A. Seizert, Valentina D. Bumbu and Vladimir B. Birman

Organic Letters 2010 Volume 12(Issue 15) pp:3472-3475

Publication Date(Web):June 29, 2010

DOI:10.1021/ol1013125

2-exo-Vinyl-7-alkylidenenorbornanes, readily prepared from fulvene Diels−Alder adducts, undergo smooth Cope rearrangement at elevated temperatures to produce hexahydroazulene derivatives.

Acyl Transfer Catalysis with 1,2,4-Triazole Anion

Co-reporter:Xing Yang and Vladimir B. Birman

Organic Letters 2009 Volume 11(Issue 7) pp:1499-1502

Publication Date(Web):March 12, 2009

DOI:10.1021/ol900098q

1,2,4-Triazole anion has been identified as an active acyl transfer catalyst suitable for the aminolysis and transesterification of esters.

Effects of Methyl Substituents on the Activity and Enantioselectivity of Homobenzotetramisole-Based Catalysts in the Kinetic Resolution of Alcohols

Co-reporter:Yuhua Zhang ;VladimirB. Birman

Advanced Synthesis & Catalysis 2009 Volume 351( Issue 14-15) pp:2525-2529

Publication Date(Web):

DOI:10.1002/adsc.200900383

Abstract

Substitution of the tetrahydropyrimidine ring in the enantioselective acyl transfer catalyst homobenzotetramisole (HBTM) 6 with methyl groups exerts a dramatic influence on its performance in the kinetic resolution of secondary alcohols. The syn-3-methyl analogue of HBTM (9a) has proved to be superior to the parent compound in terms of catalytic activity, enantioselectivity, and synthetic accessibility.

Homobenzotetramisole-Catalyzed Kinetic Resolution of -Aryl-, -Aryloxy-, and -Arylthioalkanoic Acids

Co-reporter:Xing Yang ;VladimirB. Birman

Advanced Synthesis & Catalysis 2009 Volume 351( Issue 14-15) pp:2301-2304

Publication Date(Web):

DOI:10.1002/adsc.200900451

Abstract

Effective kinetic resolutions of α-aryl-, α-aryloxy-, and α-arylthioalkanoic acids have been achieved via in situ generation of their symmetrical anhydrides and enantioselective alcoholysis in the presence of homobenzotetramisole (HBTM) 3.