Spectral data created in the course of the research project. Supports specific findings in  Synthesis of Cyclopropanes via Organoiron Methodology: Stereoselective Preparation of Bi(cyclopropyl)s .
Cyclopropanation of [2-(alkenyl)pentenediyl]Fe(CO)3 complexes (4) proceeds in a diastereoselective fashion to afford [2-(cyclopropyl)pentenediyl]Fe(CO)3. The relative stereochemistry of the products was established by X-ray crystallography. The diastereoselectivity is rationalized on approach of the cyclopropanation reagent on the sterically more exposed face of 4. Oxidatively induced reductive elimination afforded stereodefined bi(cyclopropyl)s

Chatterjee

de Meijere

Doubleday

Falck

Julia

Kasdorf

Lebel

Lukesh

Monpert

Ohno

Pietruszka

Taylor

Theberge

von Seebach

Wallock

Wang

Wilkinson

Yoshida

English

Pandey, Rajesh K.

Lindeman, Sergey V.

Donaldson, William A.

epublications@Marquette

Marquette Universitye-Publications@MarquetteNatural Products Synthesis via OrganoironMethodology Research Projects and Grants8-1-2007Spectral Data for "Synthesis of Cyclopropanes viaOrganoiron Methodology: StereoselectivePreparation of Bi(cyclopropyl)s"Rajesh K. PandeyMarquette UniversitySergey V. LindemanMarquette University, sergey.lindeman@marquette.eduWilliam A. DonaldsonMarquette University, william.donaldson@marquette.eduSynthesis of Cyclopropanes via Organoiron Methodology: Stereoselective Preparation of Biscyclopropanes Rajesh K. Pandey, Sergey Lindeman, and William A. Donaldson* Eur. J. Org. Chem. Dichlorocyclopropanation of 4a (6/7): To a solution of 4a (1.83 g, 6.27 mmol) and cetyltrimethylammonium bromide (27.6 mg, 0.076 mmol) in CHCh (40 mL) was added 50% aqueous NaOH. The biphasic mixture was vigorously stirred at room temperature for 80 h. Sl After this time, the mixture was diluted with water (50 mL), extracted several times with CH2Ch, and the combined extracts were dried (MgS04) and concentrated under reduced pressure. Analysis of the crude product by 1H NMR spectroscopy indicated this to be a mixture of 6, 7 and umeacted 4a (ca. 6: 3 : 2 by integration). Purification of the residue by column chromatography (Si02, hexanes-ethyl acetate= 96.5:3.5) gave a mixture of7 and 4a as an orange solid, followed by 6 as a yellow solid (863 mg, 2.30 mmol, 37%). Recrystallization of the mixture of7 and 4a gave crystals of 7 which were suitable for X -ray diffraction analysis. 6: mp 66-68 °C; 1H NMR (300 MHz, CDCh) o 0.26 (d, .!= 6.0 Hz, IH), 1.08-1.21 (m, 2H), 1.47 (dd,.J=5.4, 7.5 Hz, !H), 2.49 (dd,.J= 1.9, 9.1 Hz, IH), 3.03 (q,.J=6.0Hz, 1H), 3.60 (brd,.J= 6.6 Hz, 1H), 3.67 (s, 3H), 4.36 (br t,.! = 5.7 Hz, IH), 4.62 (ddd,.! = 5.7, 6.6, 9.6 Hz, IH); 13C NMR (75 MHz, CDCb) o 13.0, 26.4, 38.6, 39.8, 51.6, 54.2, 61.5, 97.9, 180.0, 203.9, 210.1, 210.6. 7: mp 130-132 oc; 1H NMR (300 MHz, CDC h) o 0.18 (d, .!= 9.0 Hz, 1H), 1.06 (t, .!= 7.2 Hz, IH), 1.18 (dt, .!= 7.5, 10.2 Hz, IH), 1.37 (dd, .!= 6.3, 9.9 Hz, IH), 2.50-2.61 (m, 1H), 2.89-2.99 (m, 1H), 3.65-3.72 (m & s, 4H total), 4.65-4.75 (m, 2H); 13C NMR (75 MHz, CDCh) o 11.4, 26.3, 38.8, 40.8, 51.7, 54.9, 59.7, 64.6, 98.3, 180.4, 203.6, 210.3, 210.6. Anal. Calcd for C13H120 5CbFe: C, 41.64; H, 3.22. Found: C, 41.69; H, 3.23. S2 (1S*,2R *,3R *,4R *)-5,5-Dichloro-1-methoxycarbonyl-2-vinylbicyclopropane (rac-11 ): To a solution of6 (400 mg, 1.07 mmol) in methanol (13 mL) at room temperature was added portion-wise eerie ammonium nitrate ( 4.1 g, 7.5 mmol) over a period of I 0 min. The mixture was stirred for an additional I 0 min and then poured into brine and extracted several times with ethyl acetate. The combined organic extracts were washed with water, followed by saturated aqueous NaHC03 and brine, dried (MgS04) and concentrated under reduced pressure to give 11 as a colorless syrup (250 mg, 1.06 mmol, 99%). 11: 1H NMR (300 MHz, CDCh) 1) 1.28-1.42 (m, 2H), 1.52 (td,.J= 4.5, 8,1 Hz, I H), 1.70 (dd, .!= 6.1, 9.4 Hz, I H), 1.90 (t,J= 4.8 Hz, I H), 2.26 (br dt, .!= 4.8, 8.1 Hz, I H), 3.74 (s, 3H), 5.19 (br d,.! = I 0.2 Hz, IH), 5.29 (br d, J = 17.1 Hz, !H), 5.63 (ddd,J = 8.1, 10.2, 17.1 Hz, !H); 13C NMR (75 MHz, CDCh) o 27.3, 27.5, 28.3, 29.0, 29.8, 52.2, 60.7, 118.4, 133.6, 173.0. Anal. Calcd for C10H120zCb:0.3H20: C, 49.94; H, 5.28. Found: C, 49.90; H, 5.16. Simmons-Smith cyclopropanation of 4c (8/9): To a solution of 4c (4.31 g, 13.4 mmol) in anhydrous CH2Ch at -20 °C was added dropwise a solution of diethylzinc in hexanes (68.4 mL, 1.0 M, 68.4 mmol) followed by diiodomethane (5.4 mL, 67 mmol). The reaction mixture was allowed to gradually warm to room temperature over a 3 h period and the mixture was stirred for an additional I h. Saturated aqueous NH4CI (70 mL) was added and mixture was diluted with ether (400 mL) and 10% aqueous HCI (70 mL). The layers were separated and the organic layer was washed with saturated aqueous Na2S03 (70 mL), followed by saturated aqueous NaHC03 (70 mL ), brine, dried (MgS04) and concentrated under reduced pressure. Analysis ofthe crude product by 1H NMR spectroscopy indicated this to be a mixture of 8 and 9 ( 4.5 : I by S3 integration). Purification of the residue by column chromatography (SiOz, hexanes~thyl acetate = 6.5:3.5) gave 9 as an orange oil followed by 8 as a red color syrup (3.15 g, 9.37 mmol, 70%). 9: IR (CHzCh) 3447,2062, 1997, 1698 cm-1; 1H NMR (300 MHz, CDCh) li 0.18 (d, J= 8.7 Hz, lH), 0.21-0.35 (m, 2H), 0.38-0.46 (m, lH), 0.80 (m, 1H), 1.70 (br s, OI-l), 2.40-2.55 (m, 2H), 3.29 (d, J= 6.3, 2H), 3.60 (d, J = 7.2 Hz, !H), 3.67 (s, 3H), 4.40-4.65 (m, 2H); 13C NMR (75 MHz, CDCh) li 9.2, 13.9, 19.2, 26.0, 43.0, 51.6, 54.5, 65.8, 66.4, 97.9, 181.0, 204.1, 210.7, 211.0. FAB-HRMS mlz 337.0363 (calcd for C14Hi706Fe (M+Hl mlz 337.0375). 8: IR (CHzCh) 3447,2067, 2002, 1698 cm-1; 1H NMR (300 MHz, CDC]]) li 0.18 (d, J= 9.0 Hz, I H), 0.19-0.30 (m, 3H), 0.90-1.00 (m, I H), 1.60 (br s, OI-l), 2.49 (m & dd, J = 2.4, 11.4 Hz, 2H total),3.30(dd,J=7.2, !!.2Hz, 1H),3.41 (dd,J=6.6., 11.1 Hz, II-!),3.61 (d,J=8.7Hz, !H), 3.67 (s, 3H), 4.50 (t, J= 7.2 Hz, !H), 4.59 (td, J= 7.7, 11.4 Hz, !H); 13C NMR (75 MHz, CDCh) li 8.1, 14.0, 20.4, 26.2, 42.9, 51.6, 54.6, 65.8, 66.6, 97.9, 181.0, 204.0, 210.6. FAB-HRMS m/z 337.0380 (calcd for C14H1706Fe (M+Hl mlz 337.0375). (1S*,2R * ,3R*,4S*,6R *)-6-Hydroxymethyl-1-methoxycarbonyl-2-vinylbicyclopropane (rac-12): To a solution of 8 (690 mg, 2.05 mmol) in methanol (24 mL) at room temperature was added portion-wise eerie ammonium nitrate (7.01 g, 12.8 mmol) over a period of 10 min. The mixture was stirred for an additional20 min and then poured into brine (30 mL) and extracted with ethyl acetate (3 x 40 mL). The combined organic extracts were washed with water (3 x 30 mL), followed by saturated aqueous NaHC03 (30 mL) and brine (30 mL), dried (MgS04) and concentrated under reduced pressure to give 12 as a colorless syrup (324 mg, 1.65 mmol, 80%). 12: IR (CH2Ch) 1726 cm-1; 1H NMR (300 MHz, CDCh) li 0.49-0.62 (m, 3H), 1.03-1.14 (m, lH), 1.45 (td,J=4.8, 9.3 Hz, !H), 1.61 (t,J=4.5 Hz, !H), 2.18 (dt,J=4.4, 9.0Hz, lH), 3.40 (dd,J=6.9, 11.1 Hz, !H), 3.50 (dd,J=6.6, ll.4Hz, !H), 3.67 (s,3I-l), 5.15 (brd,J= 10.5 Hz, !H), 5.27 (brd,J= 17.4 Hz, 1H), 5.65 (ddd,J=9.0, 10.2, 17.1 Hz, 1H); 13CNMR(75 MHz, CDCh) o 1 0.6, 14.8, 21.0, 27.0, 30.8, 31.5, 52.1, 66.6, 117.4, 134.7, 173.7. Anal. Ca1cd for C11H160J: C, 67.32; H, 8.21. Found: C, 66.94; H, 8.22. S4 ---· .15 .00 .01 .98 J L_J.LJ~ ' ' 6 5 4 3 SW/:6410 OFI: 2385.5 PW: 7.7 us PD: 1.0 see NA:S LB: 0.0 -··-C/ 6 Cl~ Me02C ''f"e(CO)J 1H NMR (300 MHz, CDC/3) .54 .08 .16 ' I 2 1 PTSid: 13132 r L PPM V> t.n 3.99 r ) I _) J I I I 7 6 5 4 STANDARD lH OBSERVE:blank line Fl: 300.136 IF2: 75.476 [SW!: 4803 I [OF!: 1804.5 EX: s2oul [PW: 6.3 us IPD: 1.0 sec INA:64 _/94 !00 I 3 2 I [PTSld: 9596 ILB: 0.0 I Cl 7 ~ -Me02C ··Fe(CO)s 1HNMR (300 MHz, CDCJ3) J'l' /98 A JUJ '--I 1 PPM USER: --DATE: Aor 20 2007 1638~ Nuts - $rkn J 4 J -lst-F-crvst.fid "" "' ~~l ~ ' ' -; ' ' ' I ' ' I ' ' ' 4 ' ' ' 6 5 STANDARD lH OBSERVEblank line Fl: 300.145 IF2: 75.479 ISWI: 4810 I IOFI: 1804.0 I EX: s2nul IPW· 6 3 usee IPD: I 0 sec INA·R 8 ' 3 I IT.R· 00 OH ~ Me02C ··Fe(COh 1HNMR (300 MHz, CDCI3) _A '-I ' ' ' I ' ' ' 2 1 PPM USER: --DATE: Jun 9 2006 IPTS!d: 16384 I I WinNuts- $rkn053-F2.fid (/) ...., J\ '._,./ I ' ' ' I ' I ' ' ' I ' ' ' I ' ' ' ' 7 6 5 4 STANDARD 1 H OBSERVE:blank line F1: 300.145 F2: 75.479 SWI:48!0 OF!: 1803.8 EX: s2 ul PW: 6.3 us PD: 1.0 sec NA:S .--' ' I ' I 3 2 LB: 0.0 OH 9 1b Me02C ''Fe(CO)a 1H NMR (300 MHz, CDCI3) \__)u ~ \.A. ' ' ' I ' I ' 1 0 PPM USER: -- DATE: Jun 9 2006 PTS!d: 14430 . 1638 ~ V> OJ .71 .89 !00 t8 7 i I i 6 5 4 3 I . ' STANDARD IH OBSERVE:blank !me IF!: 300.!36 F2: 75.476 SWI: 4803 OF!: 1803.7 lEX: s2 ul PW: 6.3 us PD: 1.0 sec NA: 8 LB: 0.0 !03 Jol JJ i 2 PTS!d: 9596 L Cl Cl~ 11 .·• ' Me02C 1HNMR (300 MHz, CDCI3) 2.68 .80 I 1 USER: PPM Vl "" 0 1'- ~ 1'- <0 1'-NN <0 r....:r....: o; v I I~ .,. ~J1 I ' ' ' -; ' ' I ' ' ' 5 ' ' ' ' I ' ' 6 4 STANDARD 1H OBSERVEblank line F1: 300.145 IF2: 75.479 ISW1: 4810 I IOFJ: 1804.4 I F.X· s2nul IPW·63 usee IPD: 1.0 sec INA8 ' I ' ' 3 I ILB: 0.0 N ~ "< ~ ~ 12 H ' ' ~ Me02C 1H NMR (300 MHz, CDCI3) I ~~ ' I ' ' ' ' 11 ' ' ' PPM1 2 USER: --DATE: Auu 9 2006 IPTSld: 16384 I I WinNuts - $rkn07l-crude fid (/) ~ 0 

Spectral Data for  Synthesis of Cyclopropanes via Organoiron Methodology: Stereoselective Preparation of Bi(cyclopropyl)s

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Synthesis of Cyclopropanes via Organoiron Methodology: Stereoselective Preparation of Bi(cyclopropyl)s

Cyclopropanation of [2-(alkenyl)pentenediyl]Fe(CO)3 complexes (4) proceeds in a diastereoselective fashion to afford [2-(cyclopropyl)pentenediyl]Fe(CO)3. The relative stereochemistry of the products was established by X-ray crystallography. The diastereoselectivity is rationalized on approach of the cyclopropanation reagent on the sterically more exposed face of 4. Oxidatively induced reductive elimination afforded stereodefined bi(cyclopropyl)s

Lindeman, Sergey

https://epublications.marquette.edu/cgi/viewcontent.cgi?article=1009&amp;context=data_nps

Spectral Data for Synthesis of Cyclopropanes via Organoiron Methodology: Stereoselective Preparation of Bi(cyclopropyl)s

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epublications@Marquette