Dalibor Sames' Retraction (from C&EN)

March 23, 2006

" A former Columbia University doctoral student, Bengü Sezen, says in an e-mail exchange with C&EN that she protests the retraction of two papers and parts of a third that she coauthored with Dalibor Sames, a chemistry professor at Columbia. The papers were published in the Journal of the American Chemical Society (2005, 126, 13244; 127, 3648 and 5284).
In her e-mail to C&EN, Sezen writes: "The reactions described in these publications were performed independently by my colleagues in my absence before the submission of papers; thus these retractions came as a surprise to me. I strongly protest that the retractions were made without my knowledge."
Sames retracted the JACS papers in written notices published in the March 8 issue of JACS (2006, 128, 3102). He says other scientists could not reproduce the results reported by Sezen.
Sezen communicated with C&EN via a Columbia e-mail address. However, she is currently listed as a Ph.D. student in the lab of molecular biology professor Elmar Schiebel at the University of Heidelberg, in Germany. She had been accepted as a postdoc in the laboratory of Chaitan Khosla, professor of chemistry, chemical engineering, and biochemistry at Stanford University. Khosla says the appointment has been "indefinitely delayed" due to the Columbia investigation.
Sezen continues: "During the past week, I have tried to contact professor Sames about [the retraction of papers] without any success. I have preserved copies of experimental data, which support the original claims of these publications, but was not given a chance to present these data. I am also prepared to perform the reactions under the supervision of professor Sames if I am given a chance."
"We were always suspicious about [Sezen], but we did not bring the matter to professor Sames because there was no smoking gun," says former Sames group member Brenton DeBoef, now a chemistry professor at the University of Rhode Island, Kingston. He says outside research groups reported that they could not reproduce her results. In the lab, "while she was there, we were able to reproduce stuff. Academic fraud is a very serious offense. I am sure the Sames group would not pursue this unless they had good evidence."
DeBoef says he smelled trouble from the time he began working in the lab as a postdoc in June 2003. At that time, he says, he set up a project with a graduate student and eight months later they had results to publish. In that time period, he says, Sezen published two papers. "It seemed too good to be true."
The retracted work concerns the selective activation of C–H bonds on a molecule, a technique commonly used to functionalize hydrocarbons. In the case of the Sames group, the technique is applied to the creation of complex organic molecules, for example, total synthesis of a natural product. The work could reduce the number of synthetic steps needed to make a given molecule, an important goal for chemists who work in the field of drug discovery.
Sames has declined to speak further with C&EN while an investigation of Sezen and her work is under way at Columbia. Sezen was awarded a Ph.D. degree in chemistry by Columbia in 2005.
DeBoef says of Sezen: "I enjoyed working with her. She's very smart. She's diligent, and she worked long hours." But DeBoef says he is troubled by reports that her work cannot be reproduced. "These reactions don't work. I am pretty sure of that. Somebody else should be able to do this. It needs to be able to be reproduced by someone else."
In a later e-mail to C&EN, Sezen lists three examples in which she says members of the Sames group did reproduce the results of her work before it was published. In all three instances, Sezen says, she was absent from the lab.
Columbia University has forbidden Sames or members of his research group to speak to the media about Sezen or the university's investigation. The scientists Sezen identified as being able to reproduce her work are both members of the Sames group. They declined to verify her assertions or otherwise speak with C&EN."

What's a Retraction

The retraction of a published science article indicates that the article should not have been published and that its data and conclusions should not be used as part of the foundation for future research. The common reasons for the retraction of articles are scientific fraud and serious error.

A Statement from G-Q Lin for his retraction of a recent JACS paper

有机所林院士的公开信
各位同事：
大家好！
可能你们已经听闻本课题组2006 年发表在JACS (2006, 128, 5624-5625)上的论文涉嫌造假一事，因该事件影响太大，其真相至今才能通报，望见谅。原因有二：其一，从发现问题到调查乃至弄清整个事件的真相需要一段不短的时间，也是一个艰难的过程，需要做许多次的反应来推敲和验证；其二，在调查和揭示真相的过程中，希望给涉嫌造假者黄凌琳一个能申辩和主动承认的缓冲时间。但遗憾的是，我们的善意未能等来她的表态。至此，我们已经按既定时间表于3 月2 日向有机所学位和学术委员会报告涉嫌造假的实情。同时，我们也已二次给JACS 主编去信，先是报告情况，然后是要求撤消该论文。黄凌琳曾是我们小组的博士研究生，她博士论文阶段的其中一个工作是研究二碘化钐诱导的2－酰基芳酸酯类化合物的不对称还原环化合成高光学纯度手性苯酞类化合物。我们期望利用手性试剂控制的不对称质子化，探讨手性苯酞的合成。经过近两年的努力，黄凌琳“实现”了这样的设想，并在进一步的研究中，发展”了非手性的质子源试剂和催化量的手性质子源试剂的组合体系，“完成”了手性苯酞的催化不对称合成，反应的对映选择性最高可达99%。其中催化部分的研究结果就发表到美国化学会志上。
黄凌琳于去年博士毕业后去了德国做博士后，苯酞研究的课题就由小组另一位研究生冯陈国同学继续。自去年9 月下旬开始，冯陈国在进行苯酞类反应的拓展实验时碰到了困难，无法取得好的结果，即以黄凌琳原来的工作为标准的模板
反应进行重复，但产率仅在30~50%，ee 值也在10~30%之间。期间，冯与已在德国的黄多次用email 联系，讨教如何操作实验，黄表示实验操作应该没有问题。
在多次实验未果的情况下，黄甚至在email 中提出 “现在我可以相信问题应该出在我一直使用的那瓶CH2I2上，估计是在那瓶中引入了一些我们所不知道的杂质，才对反应产生了效应。但遗憾的是，那瓶试剂已经被完全用光了，连瓶子都已不知去向了”，意思是说该试剂已用尽，无法找出事情的原委。同时，她还信誓旦旦地说“这些都是我当初确确实实做出来的，但现在，我也确实无法为自己做出什么有力的证明与辩护，此心唯天可证！”。事关重大，我们认为无论是何原因，都应该弄明白。就请她乘圣诞节放假之际，回所重复实验，并答应为其报销国际旅费，经过反复交涉，她同意回国。但原定12 月25 日的回国日期到了，她没有回来，只有一封email 说她在德国也重复了实验，也没有得到原先的结果，自感回来已无意义。经过多次的email 和电话联系以及交涉工作，她最终同意在春节回来。在此期间，有位自称是她男友的人来过2 次电话，提及黄顾虑重重，即表示回来与否都没有学位了。1 月21 日，她回到了上海。第二天在实验室就位，第三天开始重复自己的工作，但其实验结果与冯陈国同学的结果相差不多。
事实上，在黄回国之前，我们已经预感到问题没有这么简单，她留下来的样品中有4 个标明光学活性的化合物，虽然它们的NMR 谱是对的，但竟然是消旋体而非光活体；在同样条件下(同一台仪器、同一根手性柱以及同一位操作人员)，
测得的HPLC 数据与论文中的表述相悖。由此，我们疑窦重生，这不仅仅是重复性的问题，很可能是数据真实性的问题。在黄回国重复实验一周左右的时间、且实验结果不佳的情况下，1 月26 日上午，徐明华、黄凌琳、冯陈国和我一起开了个会。当时，黄一再表示她的数据即HPLC 和比旋肯定没有问题，我随后提出下一步由黄和冯二位一起重复催化质子源和等量质子源的实验。同时，在16 个已发表的新化合物中挑出5 个，先合成它们的消旋体，再不惜代价地用手性制备型HPLC 柱拆分，以得到其左旋与右旋体，然后与论文中的HPLC 保留时间和比旋数据进行比较。因为要完成这些工作所需的时间比较长，经过我的要求，黄同意由她本人向其德国的导师K.nig 教授请假延期返回。不料，到第三天她就借机不辞而别，她的手机也处在无人接听或关机状态。在她之后的email 中说“不要再找我了，要怎样处理，你们看着办吧，我是不会再回头了”。为了慎重起见，我们从1 月9 日起先后合成了已发表的16 个新化合物中的
11 个以及另外2 个在她博士论文中报道的，共三批样品，13 对对映异构体。在相同条件下测其HPLC 的保留时间和比旋值，并与原来的数据进行对比。结果显示，与她的数据完全不符，其中一个对映体的比旋值竟相差175 度。值得指出的是，另有2 个已知化合物，一个是用作模板反应的3-苯基取代苯酞，其图谱数据与文献一致；另一个3-甲氧基苯基苯酞的文献比旋值为8.9 度是错误的，黄报道的与错误的数据完全吻合，但实际上其比旋应该是18.5 度。由此可见，原先的数据全系造假。我们推断，虽然高ee 值苯酞化合物的NMR 谱图数据可用消旋品来代替，但在手性HPLC 上的保留时间则无法用消旋品替代，且无法知道哪个峰是代表(+)体，哪个是(-)体，更难找到一个具有同样保留时间的样品来代替真品。因而判断黄可能是用别的样品，通过适当的调配，先在HPLC 上出现二个相同的峰作为参考，再添出在手性HPLC 柱上二个大小比例相差很大的峰。因此，所给出的化合物保留时间与真品的不符。更有力的证据是，真正样品的比旋值是无法得到的，也是猜不准的，因此，造假的数据肯定也是错的。1月5 日，我们去信给JACS 主编，鉴于论文中数据的可靠性和重复性问题，正在进行调查，将尽快告之核实情况。同时，由于黄不辞而别匆忙返回德国，我
们于2 月12 日将查实情况以快递信件给她，2 月14 日快递到达她所在的大学。附信上说，我们将对比数据的结果告之，愿意给她三周的时间充分地考虑与申辩。鉴于事态的严重性和严肃性，郑重希望她认真对待，并于3 月5 日前给予答复。3 月5 日，黄在email 中说“我承认与否，还有什么区别吗？”3 月6 日，黄来电话，要求给予时间考虑，又提及承认与否有何区别？我们再三请她严肃地考虑，并在48 小时内答复。不料就此音信全无。3 月16 日，黄在德国的导师K.nig 教授在email 中告诉我们，事实上，黄在3 月初已经对他说起论文的数据有问题，因此她的聘用合同立即终止，并于3 月5 日离开了K.nig 小组。还是为了慎重起见，我们分别召开了二次组内会议，一次是在春节前由现在的小组成员组成的会议，另一次是在3 月7 日，是在沪地区已毕业的博士和已出站的博士后会议，就查核实验数据问题与大家进行了讨论，并对各种可能性进行了分析。二次组会上的讨论结果均肯定她论文中关于手性苯酞合成的部分是造假无疑。虽然黄煞费苦心，从表面上看，近20 个化合物的核磁、红外、质谱、HPLC谱以及比旋的数据均齐全，但最终谎言还是被戳穿！令我非常痛心的是，她为什么要造假？！我深知学生们十数年寒窗之不易，因而对待学生如同己出，从没有不切实际的要求，尽量营造一个宽松的研究氛围。更让我寒心的是，在真实的数据面前，黄凌琳不但没有直面它，而是采取赌咒发誓、错误引导、百般抵赖、直至销声匿迹的态度。她还曾在email 里说“这个反应我怎么可能在这么长的时间内作出这样的弥天谎言呢？”事实上，自她捏造第一个化合物的数据起，就决定着她要为此不断地说谎和圆谎，还要不断地察言观色，为造假备受煎熬。甚至在临毕业前，在指定学生在场的情况下复核实验以及其它的一系列检查等措施中，设法侥幸逃脱。但最终还是会被揭露的。其实，她大可不必如此，只要她认认真真、踏踏实实地做实验，就能够毕业的，犯不着拿自己的前程做赌注。造假终究会水落石出的，也必定会付出巨大的代价。她的造假，不仅是毁了她自己，也毁了我和小组的良好声誉，更可能会影响到小组现在的学生，尤其是冯陈国同学半年多的宝贵时间付之东流；她的造假，对我是一个深深的、不光彩的伤痛，对徐明华博士是挥之不去的噩梦，对我们小组更是永远的烙印。这是个沉痛的教训，但愿警钟长鸣！事已至此，我只能选择面对，而不是掩盖和包庇。我必须公布真相，以杜绝此类事件的再度发生。我们已于3 月15 日给JACS 的主编去信，要求撤消JACS上的那篇论文；于3 月22 日向有机所学位和学术委员会报告造假实情；相关情况也已于3 月23 日通报本所所有的在读研究生。现在所学位委员已成立调查小
组，展开调查，将尽快核实并根据情节提议通报国务院学位办，撤消黄凌琳的理学博士学位。因管教不严造成如此严重后果而深感内疚的我由衷地向有机所全体研究人员和研究生致歉。但我相信，我们以实事求是的态度来昭示此事是正确的。诚信为本，揭示造假的手段也是对杜绝造假的一种威慑。进而，我们仍将继续努力工作，去探索科学的真理，在基础研究领域中做出好的成绩、发表质量高的论文。与大家共勉。
* 附件是消旋体经手性拆分后得到的(+)和(-)体与JACS 论文上的比旋数据的比较。
林国强
2007 年3 月26 日

G Wang-J. Phy. Chem. Sol 2005

The paper was retracted in July 2006,Journal of Physics and Chemistry of Solids, v. 67, iss. 7, p. 1605.
Retraction Reason:
Originally Published:
Journal of Physics and Chemistry of Solids, Vol 66, Issue 6, June 2005, pp. 1107-1111
Title:
Effect of F- ions on spectroscopic properties of Yb3+-doped zinc-tellurite glasses
Authors:
G Wang, J Zhang, S Dai, J Yang and Z Jiang
Affliation:
Abstract:

K. R. Flower-Angew Chem Int Ed 2006

This article was retracted on : November 20, 2006, Angew. Chem. Int. Ed 45,7489, 2006.
Retraction Reason:
Since publication of this Communication, it has come to the authors’ attention that the crystallographically determined structure of [NEt4][HgCl2][HgCl3] has been described previously (Acta Cryst. E 2002, 58, m534). The cell parameters and structural data are consistent with those of the compound that the authors reported as being [NEt4]-[AuCl2][AuCl3]. Clearly the structure of the mercury compound as an impurity in the reaction product has been determined. Thus, all the conclusions drawn from this data
are invalid, although several gold-containing products were derived from the reaction in high overall yields. Accordingly, the authors withdraw this Communication, apologize for these mistakes and that the readership of Angewandte Chemie has been misled by
the publication of this Communication. They would like to thank Prof. H. Schmidbaur for initially drawing their attention to this matter.
Originally Published:
Angew. Chem. Int. Ed. 2006, 45, 6535-6537
Title:
[NEt4][AuCl2][AuCl3]: Solid-State Evidence of Essentially Y-Shaped Jahn–Teller-Distorted AuCl3
Authors:K. R. Flower,* R. G. Pritchard, A. T. McGown
Affiliation:
School of Chemistry, University of Manchester,UK
Abstract:

N.M.Patil-Chem Commun 2003

This paper was retracted on 27th September 2004.
Retraction Reason:
We, the named authors, hereby wholly retract this Chemical Communication.Signed: Nandkumar M. Patil, Ashutosh A. Kelkar, Zahid Nabi and Raghunath V. Chaudhar, Pune, India, September 2004.Retraction endorsed by Sarah Thomas, Managing Editor. Retraction published 27th September 2004.
Originally Published:
Chem. Commun., 2003, 2460 - 2461.
Title:
Novel CuI/tributyl phosphine catalyst system for amination of aryl chlorides
Authors:
Nandkumar M. Patil, Ashutosh A. Kelkar, Zahid Nabi and Raghunath V. Chaudhari
Affiliation:
Abstract:

T. L. Makarova-Nature 2001

This paper was retracted on 30 March 2006 Nature 440, 707, 2006.
Retraction Reason:
In this Letter we reported high-temperature ferromagnetism in a polymeric phase of pure carbon that was purportedly free of ferromagnetic impurities1. Since then, however, measurements made on the same and similar samples using particle-induced X-ray emission (PIXE) with a proton microbeam have indicated that these had considerable iron content. Also, polymerized C60 samples mixed with iron before polymerization had a similar Curie temperature (500 K) to those we described1, owing to the presence of the compound Fe3C (cementite). In addition, it has since been shown that the pure rhombohedral C60 phase is not ferromagnetic.
Nevertheless, magnetic order in impurity-free graphitic structures at room temperature has been demonstrated independently(before and after publication of ref. 1). Ferromagnetic properties may yet be found in polymerized states of C60 with different structural defects and light-element (H, O, B, N) content.
T.L.M. and P.S. decline to sign this retraction because they do not believe that the earlier results1, supported in subsequent studies, are totally invalidated by these findings.
Originally Published:
Nature 413, 716–718 (2001)
Title:
Magnetic carbon
Authors:
T. L. Makarova*, B. Sundqvist, R. Höhne, P. Esquinazi, Y. Kopelevich, P. Scharff, V. Davydov, L. S. Kashevarova and A. V. Rakhmanina
Affiliation:
Ioffe Physico-Technical Institute,Russia
Department of Experimental Physics, Umeå University,Sweden
Institute for Physics, Chemical Department, TU Ilmenau, Germany
Abstract:

Guo-Qiang Lin-J. Am. Chem. Soc 2006

This paper has been requested to be retracted.
Retraction Reason:
Originally Published:
J. Am. Chem. Soc., 128 (17), 5624 -5625, 2006.
Title:
Catalytic Enantioselective Synthesis of Chiral Phthalides by SmI2-Mediated Reductive Cyclization of 2-Acylarylcarboxylates
Authors:
Ling-Lin Huang, Ming-Hua Xu,* and Guo-Qiang Lin*
Affiliation:
Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences, and Shanghai Institute of Materia Medica (SIMM), Chinese Academy of Sciences, China
Abstract:

F.-S. Xiao-Angew. Chem. Int. Ed. 2005

This paper was retracted on 1 Sep 2006, Angew. Chem. Int. Ed. 2006, 45 (35), 5729-5729.
Reaction Reason:
After the publication of this Communication the authors have noticed that the scale bars on some of the TEM images are wrong. The particle size data extracted from these images is thus incorrect and the conclusions drawn from this data are therefore invalid. Accordingly, all the authors withdraw this Communication. They apologize for these mistakes and that the readershipof Angewandte Chemie has been misled by the publication of this Communication.
Originally Published:
Angew. Chem. Int. Ed. 2005, 44, 2563–2568
Title:
Design and Size Control of Uniform Zeolite Nanocrystals Synthesized in Adjustable Confined Voids Formed by Recyclable Monodisperse Polymer Spheres
Authors:
X. Yang, Y. Feng, G. Tian, Y. Du, X. Ge, Y. Di, Y. Zhang, B. Sun, F.-S. Xiao*
Affiliation:
Department of Chemistry & Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, China
Abstract:

D Sames-J. Am. Chem. Soc. 2003

This paper was retracted on June 21, 2006 J. Am. Chem. Soc., 128 (25), 8364 -8364, 2006.
Retraction Reason:
After the departure of the first author and during a thorough re-examination of this publication, the laboratory of the corresponding author (D. Sames) has been unable to reproduce some of the key results. Specifically, the magnesium oxide method gave no arylation products (Scheme 1 and Scheme 4). The C-2' arylation procedures described in this publication (Scheme 2) did furnish the desired products, but with lower efficiency than originally claimed. Namely, 2-phenyl imidazole 1, under the action of CpRu(Ph3P)2Cl catalyst and Cs2CO3 base, gave product 2 in 23% isolated yield (see scheme below; 84% yield was reported in the original publication). C-2' phenylation of 1,2-diphenylimidazole (Scheme 5), catalyzed by Rh(acac)(CO)2, provided <10% of the desired product (GC yield; 81% yield was originally reported). Accordingly, the corresponding author withdraws this paper, and deeply regrets that the chemical community was misled by this publication.
Title:
Diversity Synthesis via C-H Bond Functionalization: Concept-Guided Development of New C-Arylation Methods for Imidazoles
Originally Published:
J. Am. Chem. Soc. 2003, 125, 10580-10585
Authors:
Bengu Sezen and Dalibor Sames*
Affiliation:
Columbia University
Abstract:

D Sames-J. Am. Chem. Soc. 2003

This paper was retracted on June 21, 2006J. Am. Chem. Soc., 128 (25), 8364 -8364, 2006.
Retraction Reason:
After the departure of the first author, the laboratory of the corresponding author (D. Sames) has been unable to reproduce the key results of this paper. Although the formation of indole magnesium salts, by treatment with either Grignard reagents or Mg(HMDS)2, is a viable strategy for C-arylation of indoles as described and confirmed elsewhere,1 the procedure using MgO as the base gave no arylation products. Accordingly, the corresponding author withdraws this paper, and deeply regrets that the chemical community was misled by this publication. (1) Lane, B. S.; Brown, M. A.; Sames, D. J. Am. Chem. Soc. 2005, 127, 8050-8057.06/21/2006
Originally Published:
J. Am. Chem. Soc. 2003, 125, 5274-5275
Title: Selective C-Arylation of Free (NH)-Heteroarenes via Catalytic C-H Bond Functionalization
Authors:Bengu Sezen and Dalibor Sames*
Affiliation: Columbia University
Abstract:

D Sames-J. Am. Chem. Soc. 2005

This paper was retracted on March 1, 2006 J. Am. Chem. Soc., 128 (9), 3102 -3102,
Retraction Reason:
After the departure of the first author, the laboratory of the corresponding author (D. Sames) has been unable to reproduce the key results in this publication. Accordingly, the corresponding author withdraws this paper, and deeply regrets that the chemical community was misled by its publication.03/01/2006
Originally Published: J. Am. Chem. Soc. 2005, 127, 5284-5285
Title: Selective and Catalytic Arylation of N-Phenylpyrrolidine: sp3 C-H Bond Functionalization in the Absence of a Directing Group
Authors: Bengu Sezen and Dalibor Sames*
Affiliation: Columbia University
Abstract:

D Sames-J. Am. Chem. Soc. 2002

This paper was withdrawn on June 21, 2006, J. Am. Chem. Soc., 128 (25), 8364 -8364,
Retraction Reason:The laboratory of the corresponding author (D. Sames) has not been able to reproduce this work. Accordingly, the second and third authors withdraw this paper, and they deeply regret that the chemical community was misled by this publication.06/21/2006
Originally Published: J. Am. Chem. Soc. 2002, 124, 13372-13373
Title: C-C Bond Formation via C-H Bond Activation: Catalytic Arylation and Alkenylation of Alkane Segments
Authors: Bengu Sezen, Roberto Franz, and Dalibor Sames*
Affiliation: Columbia University
Abstract:

T Ishikawa & S Saito-J. Am. Chem. Soc. 2001

This paper was corrected on September 7, 2001, J. Am. Chem. Soc., 123 (39), 9724 -9724.
Retraction Reason:
We have recently become aware of the presence of two previouus papers by Davies1 very closely related to our work entitled "Novel [2,3]-Sigmatropic Rearrangement for Carbon-Nitrogen Bond Formations" recently published in this journal.2 These two previous papers are clearly indicating that the discovery of [2,3]-sigmatropic rearrangement of this class must be credited to Davies.1 Our insufficient literature search is surely responsible for this serious matter. Therefore, it is appropriate that we should retract our recent paper2 concerned with this chemistry. (1) (a) Davies, S. G.; Jones, S.; Sanz, M. A.; Teixeira, F. C.; Fox, J. F. Chem. Commun. 1998, 2235-2236. (b) Bull, S. D.; Davies, S. G.; Jones, S.; Ouzman, J. V. A.; Price, A. J.; Watkin, D. J. Chem. Commun. 1999, 2079-2080. (2) Ishikawa, T.; Kawakami, M.; Fukui, M.; Yamashita, A.; Urano, J.; Saito, S. J. Am. Chem. Soc. 2001, 123, 7734-7735. Our first manuscript having the same title as this paper covering the content of ref 1a was submitted to this journal on September 21, 1998, whereas Davies submitted his first manuscript (ref 1a) to Chem. Commun. on August 5, 1998. These records are consistent with the idea that Davies and we were independently concerned with the same chemistry at the same time.09/07/2001
Originally Published: J. Am. Chem. Soc. 2001, 123, 7734-7735.
Title: Novel [2,3]-Sigmatropic Rearrangement for Carbon-Nitrogen Bond Formation
Authors: Teruhiko Ishikawa,* Masatomo Kawakami, Miyuki Fukui, Ayako Yamashita, Jin Urano, and Seiki Saito*
Affiliation:
Abstract:
[2,3]-Sigmatropic rearrangement is a widespread method for regiospecific carbon-carbon or carbon-heteroatom bond formation in organic synthesis,1 and enormous examples have been reported including their applications to asymmetric synthesis and natural product synthesis. For aza-versions,2 a number of allylchalcogenide and allylamineimide derivatives have been demonstrated to be usable for transferring amino groups to allylic positions (Scheme 1). However, more simple and efficient methods for the construction of allylic amines from allylic alcohols are desirable.3 And our recent studies on hydroxylamine-based chemistry4 have led us to the discovery of novel [2,3]-sigmatropic rearrangement of O-allylic hydroxylamines in which a negatively charged nitrogen atom is a migration terminus (Scheme 1). In this paper we detail the features of such a [2,3]-sigmatropic rearrangement as a highly useful method for the synthesis of N-hydroxyallylamines, precursors for allylic amines, a biologically important class of compounds.

Dalibor Sames-J. Am. Chem. Soc., 2005

This paper was corrected on January 3, 2007 (J. Am. Chem. Soc. 2007, 129, 241).
Retraction (correction) Reason:
For comparison purposes, this article refers to a palladium-catalyzed arylation of free azoles in the presence of magnesium oxide, published previously in a separate communication. Although the magnesium oxide procedure has recently been found irreproducible (J. Am. Chem. Soc. 2006, 128, 8364), this fact does not affect the conclusions of this paper. Consequently, the magnesium oxide protocol has been removed from the Supporting Information. Also, Figures S5 and S8 have been replaced with corrected versions.
Originally Published:
J. Am. Chem. Soc. 2005, 127, 8050-8057
Title:
Direct Palladium-Catalyzed C-2 and C-3 Arylation of Indoles: A Mechanistic Rationale for Regioselectivity
Authors:Benjamin S. Lane, Meghann A. Brown, and Dalibor Sames *
Affiliation:Department of Chemistry, Columbia University, New York.
Abstract:

Dalibor Sames-J. Am. Chem. Soc., 2004

This paper was retracted on March 1, 2006 (J. Am. Chem. Soc. 2006, 128, 3102).
Retracted Reason:
Originally Published:
J. Am. Chem. Soc., 126 (41), 13244 -13246, 2004.
Title:
Oxidative C-Arylation of Free (NH)-Heterocycles via Direct (sp3) C-H Bond Functionalization
Authors:
Bengü Sezen and Dalibor Sames*
Affiliation:
Department of Chemistry, Columbia University, New York.
Abstract: