Donaldson, William

Yun, Young K.

English

Donaldson, William A.

epublications@Marquette

Marquette Universitye-Publications@MarquetteChemistry Faculty Research and Publications Chemistry, Department of4-1-1997An Unusual Stereochemical Outcome in theOxidatively Induced Reductive Elimination of(Pentenediyl)iron ComplexesYoung K. YunWilliam DonaldsonMarquette University, william.donaldson@marquette.eduAccepted version. Journal of the American Chemical Society, Volume 119, No. 17 (1997), DOI. ©1997 American Chemical Society. Used with permission.NOT THE PUBLISHED VERSION; this is the author’s final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page. Journal of the American Chemical Society, Vol 119, No. 17 (1997): pg. 4084-4085. DOI. This article is © American Chemical Society and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society. 1     An Unusual Stereochemical Outcome in the Oxidatively Induced Reductive Elimination of (Pentenediyl)iron Complexes   Young K. Yun Department of Chemistry, Marquette University, Milwaukee, WI William A. Donaldson Department of Chemistry, Marquette University, Milwaukee, WI     Oxidatively induced reductive elimination is an important reaction step in numerous stoichiometric and catalytic transition metal mediated carbon−carbon bond formations. This process is well-known to occur with retention of stereochemistry.1 We2 and others3 have reported that the oxidative decomplexation of (pentenediyl)iron complexes bearing an electron-withdrawing substituent provides a novel methodology to generate vinylcyclopropanes.4 We herein report on an unexpected stereochemical outcome for certain substrates and propose a mechanism to account for these results.  NOT THE PUBLISHED VERSION; this is the author’s final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page. Journal of the American Chemical Society, Vol 119, No. 17 (1997): pg. 4084-4085. DOI. This article is © American Chemical Society and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society. 2  We have previously reported that the reaction of tricarbonyl(1-(methoxycarbonyl)pentadienyl)iron(1+) cation with malonate anions occurs regioselectively at an internal position (C2) to give stable (pentenediyl)iron complexes 1a−c.6 The relative stereochemistry of 1a and 1b were established by X-ray diffraction analysis.6 Oxidative decomplexation of 1a with cerium ammonium nitrate (CAN, 10 equiv, DMF or MeOH) generates the vinylcyclopropane 2a as the major product (Table 1; entry 1). This result is consistent with an oxidatively induced reductive elimination occuring with retention of stereochemistry. In comparison, oxidation of 1a with trimethylamine N-oxide (TMANO, C6H6, reflux) gave a mixture of diastereomeric vinylcyclopropanes 2a, 3a, and 4a (Table 1; entry 2). The relative stereochemistries of 2a, 3a, and 4a are based on their 1H NMR spectral data.7 In particular, the ring protons of each with a cis relationship are coupled by ca. 9 Hz, while ring protons with a trans relationship are coupled by ca. 5−6 Hz.8 It is important to note that vinylcyclopropane 2a does not isomerize to 3a or 4a upon treatment with either TMANO or triethylamine (C6H6, 80 °C). Thus, the products 3a and 4a are not the result of rearrangement or epimerization of 2a.     NOT THE PUBLISHED VERSION; this is the author’s final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page. Journal of the American Chemical Society, Vol 119, No. 17 (1997): pg. 4084-4085. DOI. This article is © American Chemical Society and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society. 3  Table 1. Oxidative Decomplexation of (Pentenediyl)iron Complexes (E = CO2Me; a, R = H; b, R = Me; c, R = OMe)   entry R conditions product ratio (2:3:4) total yield (%)  1  H (a)  CAN/DMF/23 °C  10:1:0  70  2  H (a)  TMANO/C6H6/80 °C  2:4:1  69  3  Me (b)  CAN/DMF/23 °C  0:1:0  55  4  Me (b)  TMAO/C6H6/80 °C  0:1:0  56  5  OMe (c)  CAN/DMF/23 °C  0:1:0  25  In sharp contrast, oxidative decomplexation of 1b with either CAN or TMANO gave only 3b (Table 1; entries 4 and 5). The relative stereochemistry of vinylcyclopropane 3b was tentatively assigned on the basis of its 1H NMR spectral data.7 In particular, the vinylic methine proton of 3b appears at δ 6.14 ppm, while those of vinylcyclopropanes 2a, 3a, and 4a appear at δ 5.26, 6.07, and 5.13 ppm, respectively. This tentative assignment was subsequently confirmed by X-ray diffraction analysis9 of a crystalline derivative (5b) prepared in an unambiguous fashion (eq 1). Similarly, the oxidative decomplexation of 1c gave 3c (25%) along with recovered starting material (25%) (Table 1; entry 5). The structure of 3c was assigned by comparision of its 1H NMR spectral data with that of 3b. The vinylcyclopropanes 3b and 3c represent oxidatively induced reductive elimination of 1b and 1c with apparent inversion of configuration at C3.   NOT THE PUBLISHED VERSION; this is the author’s final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page. Journal of the American Chemical Society, Vol 119, No. 17 (1997): pg. 4084-4085. DOI. This article is © American Chemical Society and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society. 4  The following mechanism is proposed to rationalize these results (Scheme 1). Oxidation of pentenediyl complex 1 leads directly to the species 6. A π−σ−π rearrangement of 6 via the metallocyclohexene intermediate 8 generates the species 7 with inversion of configuration at C3 (with respect to the configurations at C1 and C5).10 Reductive elimination of 6, with retention of configuration, leads to vinylcyclopropanes 2. For products 3, the apparent inversion of configuration results from π−σ−π rearrangement followed by reductive elimination (i.e., inversion followed by retention). For 6a (R = H) at 23 °C, the π−σ−π rearrangement is slow with respect to reductive elimination; however, at higher reaction temperatures the rearrangement becomes rapid enough to allow for the formation of both 2a and 3a. In comparison, rearrangement of 6b to 7b (R = Me) is rapid compared to reductive elimination. It should be noted that the malonate substitutent occupies a pseudoaxial position and the C1 ester a pseudoequatorial position in 6 (cf., the X-ray crystal structures6 of 1a and 1b) while in 7 the malonate substitutent occupies a pseudoequatorial position and the C1 ester a pseudoaxial position. The equilibrium between 6b and 7b lies farther in the direction of 7b than does the equilibrium between 6a and 7a, due to the greater steric bulk of the dimethyl methylmalonate substituent.10   Scheme 1  NOT THE PUBLISHED VERSION; this is the author’s final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page. Journal of the American Chemical Society, Vol 119, No. 17 (1997): pg. 4084-4085. DOI. This article is © American Chemical Society and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society. 5  It is proposed that the π−σ−π rearrangement of the pentenediyl complexes occurs readily only for the oxidized species 6/7.11 (Pentenediyl)iron complex 1a is recovered unchanged under the reaction conditions of entry 1 or 2 in the absence of oxidant (DMF/23 °C/18 h or C6H6/80 °C/4 h), and 1b was recovered unchanged upon stirring to conditions in entry 3 in the absence of oxidant (DMF/18 h/23 °C). If the 18-electron pentenediyl complexes 1a or 1b undergo π−σ−π rearrangement at these conditions, these equilibria must lie far in the direction of the 1a and 1b, since no diastereomeric pentenediyl complexes are observed under the reaction conditions, in the absence of oxidant. Furthermore, when the oxidation of 1a (CAN/DMF/23 °C or TMANO/C6H6/80 °C) was carried to less than completion, the unreacted 1a was recovered unchanged, in addition to the vinylcyclopropane products.  It may be noted that the π−σ−π rearrangement of 6 to 7 occurs with inversion of the exo-endo stereochemistry at the σ-bound end of the allylic portion of 6. If the proposed mechanism is valid, this inversion of stereochemistry should be reflected in the products. Toward this end, the deuterium-labeling studies were carried out. The stereoselectively deuterium-labeled cation 11 was prepared from 9 (Scheme 2) in a fashion similar to our previous preparation of the stereoselectively labeled cation 12.12 Cation 11, prepared by this method, was found to possess the deuterium label 75% in the exo-position and 25% in the endo-position, by integration of its 1H NMR spectrum. Reaction of 11 with dimethyl malonate or dimethyl methylmalonate anion gave predominantly13 the pentenediyl complexes d-1a and d-1b in which deuterium was located 75% in the exo-position (Scheme 3).   Scheme 2  NOT THE PUBLISHED VERSION; this is the author’s final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page. Journal of the American Chemical Society, Vol 119, No. 17 (1997): pg. 4084-4085. DOI. This article is © American Chemical Society and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society. 6   Scheme 3  The oxidative decomplexation of d-1a (CAN/DMF/23 °C) gave d-2a; 1H NMR integration of the vinyl methylene protons indicated the product to be 72% E (Scheme 3). In comparison, oxidative decomplexation of d-1b (CAN/DMF/23 °C) gave d-3b; 1H NMR integration of the vinyl methylene protons indicated the product to be 75% Z (Scheme 3). Finally, the oxidative decomplexation of d-1a (TMANO/C6H6/80 °C) gave a mixture of d-2a and d-3a (1:2). Analysis of the mixture indicated that d-2a was 71% E while d-3a was 66% Z. Thus, inversion of configuration at the vinylcyclopropyl carbon is accompanied by an inversion in the stereochemistry about the C C double bond. These results are consistent with the mechanism proposed in Scheme 1.  We are currently examining the application of this methodology for the preparation of cyclopropyl-containing natural products.    NOT THE PUBLISHED VERSION; this is the author’s final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page. Journal of the American Chemical Society, Vol 119, No. 17 (1997): pg. 4084-4085. DOI. This article is © American Chemical Society and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society. 7  Acknowledgment Financial support for this work was provided by the National Institutes of Health (GM-42641). High-resolution mass-spectral determinations were made at the Nebraska Center for Mass Spectrometry. The authors thank Mr. Victor G. Young, Jr. (University of Minnesota) for obtaining the X-ray crystal structure of 5b and Dr. Alain Krief (Universitaires Notre-Dame de la Paix, Belgium) for helpful discussions. Supporting Information Available Experimental details and spectroscopic data (7 pages). See any current masthead page for ordering and Internet access instructions. References 1Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principle and Application of Organotransition metal Chemistry; University Science Books:  Mill Valley, CA, 1987. 2Donaldson, W. A.; Ramaswamy, M. Tetrahedron Lett. 1989, 30, 1339−42. 3Saber, S. P.; Slawin, A. M.; Thomas, S. E.; Williams, D. J.; Ward, M. F.; Worthington, P. A. J. Chem. Soc., Chem. Commun. 1994, 2169−70. Jandeleit, B. Ph.D. Dissertation, Rheinisch-Westfälischen Technischen Hochschule Aachen, Germany, 1995. 4The reverse process, formation of (pentenediyl)Fe(CO)3 complexes from the reaction of vinylcyclopropanes with Fe(CO)5, has been reported.5 However, since the iron species generated as a byproduct in the present case is not Fe(CO)5, it can not be assumed that these reactions follow the same reversible reaction pathway. 5Aumann, R. J. Am. Chem. Soc. 1974, 96, 2631−2. Schulze, M. M.; Gockel, U. Tetrahedron Lett. 1996, 37, 357−8. Schulze, M. M.; Gockel, U. J. Organomet. Chem. 1996, 525, 155−8. 6Donaldson, W. A.; Shang, L.; Tao, C.; Yun, Y. K.; Ramaswamy, M.; Young, V. G. J. Organomet. Chem. 1997, in press. 7Selected 300 MHz 1H NMR spectral data (C6D6). For 2a:  δH 5.26 (ddd, J = 7.5, 9.9, 17.1 Hz, 1H), 4.93 (d, J = 17.1 Hz, 1H), 4.88 (d, J = 11.4 Hz, 1H), 3.27, 3.26, and 3.25 (3 s, 9H), 3.04 (d, J = 11.0 Hz, 1H), 2.57 (ddd, J = 4.9, 9.6, 11.1 Hz, 1H), 2.33 (dt, J = 4.9, 8.5 Hz, 1H), 1.76 (apparent t, J = 4.9 Hz, 1H). For 3a:  δH 6.07 (ddd, J = 9.2, 10.2, 17.2 Hz, 1H), 5.16 (dd, J = 1.2, 17.1 Hz, 1H), 4.99 (dd, J = 1.2, 10.2 Hz, 1H), 3.26, 3.22, and 3.21 (3 s, 9H), 2.73 (d, J = 9.8 Hz, 1H), 2.53 (ddd, J = 5.4, 6.1, 9.8 Hz, 1H), 1.88 (dd, J = 5.3, 9.1 Hz, 1H), 1.71 (dt, J = 6.2, 9.1 Hz, 1H). For 4a:  δH 5.13 (ddd, J = 7.6, 10.0, 17.3 Hz, 1H), 4.97 (dd, J = 1.7, 17.3 Hz, 1H), 4.80 (dd, J = 1.7, 10.0 Hz, NOT THE PUBLISHED VERSION; this is the author’s final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page. Journal of the American Chemical Society, Vol 119, No. 17 (1997): pg. 4084-4085. DOI. This article is © American Chemical Society and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society. 8  1H), 4.23 (d, J = 10.7 Hz, 1H), 3.30, 3.25, and 3.23 (3 s, 9H), 2.18 (br q, J = 6.3 Hz, 1H), 1.99 (ddd, J = 6.3, 8.8, 10.8 Hz, 1H), 1.82 (dd, J = 5.0, 8.9 Hz, 1H). For 3b:  δH 6.14 (ddd, J = 8.8, 10.2, 17.1 Hz, 1H), 5.18 (dd, J = 1.8, 17.1 Hz, 1H), 5.02 (dd, J = 1.8, 10.2 Hz, 1H), 3.31, 3.22, and 3.21 (3 s, 9H), 2.61 (dd, J = 5.9, 6.6 Hz, 1H), 2.18 (dd, J = 5.9, 9.3 Hz, 1H), 2.00 (dt, J = 6.7, 9.0 Hz, 1H), 1.23 (s, 3H). 8Silverstein, R. M.; Bassler, G. C.; Morrill, T. C. Spectrometric Identification of Organic Compounds; John Wiley & Sons, Inc.:  New York, 1991. 9Young, V. G., Jr.; Yun, Y. K.; Donaldson, W. A. Submitted. 10The difference in the steric sizes of the dimethyl malonate substituent present in 1a and the dimethyl methylmalonate substituent present in 1b is manifested in a considerably larger C4−C3−C2−C7 torsional angle for 1b (81.3°) compared to 1a (65.3°) in the crystal state.6 11Notably, syn-anti isomerization of (π-allyl)Fe(CO)4+ cations (18-electron complexes) via a π−σ−π mechanism requires heating (60 °C) for extended periods of time (36−144 h). Gibson, D. H.; Erwin, D. K. J. Organomet. Chem. 1975, 86, C31−C33. Salzer, A.; Hafner, A. Helv. Chim. Acta 1983, 66, 1774−85. 12Donaldson, W. A.; Shang, L.; Ramaswamy, M.; Droste, C. A.; Tao, C.; Bennett, D. W. Organometallics 1995, 14, 5119−26. 13The reaction of lithium dimethyl malonate with (1-(methoxycarbonyl)pentadienyl)Fe(CO)3+ gave 1a and a minor amount of diene complex i (20:1).4 The reaction of 11 with lithium dimethyl malonate gave d-1a and d-ia(6:1), while reaction of 11 with lithium dimethyl methylmalonate gave d-1b and d-ib (8:1). This increase in the ratio of attack at C5 vs C2 is attributed to an inverse α-secondary isotope effect.   

An Unusual Stereochemical Outcome in the Oxidatively Induced Reductive Elimination of (Pentenediyl)iron Complexes

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An Unusual Stereochemical Outcome in the Oxidatively Induced Reductive Elimination of (Pentenediyl)iron Complexes

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