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Wednesday, 17 February 2016

cis (Z) jasmone



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 cis (Z) jasmone 
(Can. J. Chem. 1978, Vol 56, p2301)


e.g. How might we attempt to make Z jasmone – an important constituent of many perfumes?

In fact one synthesis uses the following as carbon sources:
It is not clear from this however, how the chemistry might be done!  Therefore just being given the starting materials is not sufficient to help plan a synthesis.
Note the importance of CCBFR.
We need a logical planning method.
Retrosynthetic Analysis (The Disconnection Approach)
Originated by E.J. Corey (Nobel Prize 1990)               p169 – 172
                                                                                    p259 – 260
                                                                                    p354 – 359

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Sunday, 14 February 2016

Interesting compound, Spoked-wheel macrocycles

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  • Chemical Formula: C774H996N18O36Si12
  • Molecular Weight: 11465.32
  • Elemental Analysis: C, 81.08; H, 8.76; N, 2.20; O, 5.02; Si, 2.94
 4-({2-[4-(2-{9-[4-(4-{2-[2,5-Bis(octyloxy)-4-(2-{4-[pentakis({4-[2-(4-{2-[4-(4-{2,7-bis[2-(4-{2-[(3-cyanopropyl)bis(propan-2-yl)silyl]ethynyl}-2,5-bis(octyloxy)phenyl)ethynyl]-9H-carbazol-9-yl}phenyl)phenyl]ethynyl}-2,5-bis(octyloxy)phenyl)ethynyl]phenyl})phenyl]phenyl}ethynyl)phenyl]ethynyl}phenyl)phenyl]-7-[2-(4-{2-[(3-cyanopropyl)bis(propan-2-yl)silyl]ethynyl}-2,5-bis(octyloxy)phenyl)ethynyl]-9H-carbazol-2-yl}ethynyl)-2,5-bis(octyloxy)phenyl]ethynyl}bis(propan-2-yl)silyl)butanenitrile


Compound 7

From Fluctuating exciton localization in giant π-conjugated spoked-wheel macrocycles

Nature Chemistry5,964–970
doi:10.1038/nchem.1758
Supplementary Information
 

C774H996N18O36Si12
Name compound: 4-({2-[4-(2-{9-[4-(4-{2-[2,5-Bis(octyloxy)-4-(2-{4-[pentakis({4-[2-(4-{2-[4-(4-{2,7-bis[2-(4-{2-[(3-cyanopropyl)bis(propan-2-yl)silyl]ethynyl}-2,5-bis(octyloxy)phenyl)ethynyl]-9H-carbazol-9-yl}phenyl)phenyl]ethynyl}-2,5-bis(octyloxy)phenyl)ethynyl]phenyl})phenyl]phenyl}ethynyl)phenyl]ethynyl}phenyl)phenyl]-7-[2-(4-{2-[(3-cyanopropyl)bis(propan-2-yl)silyl]ethynyl}-2,5-bis(octyloxy)phenyl)ethynyl]-9H-carbazol-2-yl}ethynyl)-2,5-bis(octyloxy)phenyl]ethynyl}bis(propan-2-yl)silyl)butanenitrile.

 https://www.instagram.com/p/BBMfA4bBkvZY9QhsJV6ff6khLjUE6F9MqBqRu40/

  • Synthetic Procedure: See article for the definitive version of this procedure and for full experimental details.6 (19.0 mg, 14.7 µmol), CuI (3.4 mg, 17.7 µmol), Pd2dba3(4.0 mg, 4.4 µmol), and tri(t‑butyl)phosphine (6.0 mg, 29.5 µmol) were mixed in a microwave tube and sealed with a septum. In parallel, a solution of 5 (241.7 mg, 132.6 µmol) in piperidine (2 mL) was purged with argon for 1 h. Then the latter was transferred to the microwave tube and the mixture was heated at 120 °C for 16 min in a microwave instrument (max. power: 300 W). After cooling to r.t., the tube was opened and the reaction mixture was diluted with MTBE. The organic phase was washed with aq. H2SO4 (10 %) and brine. It was dried over MgSO4 and the solvent was removed under reduced pressure. The residue was purified by column chromatography (CH:DCM = 65:35 ‑ 68:32), and 7 (126 mg, 10.9 µmol, 74 %) was obtained as a yellow solid. 1H NMR (500 MHz, CDCl3, 298 K) δ [ppm] = 8.09 (d, 3JH,H = 8.2 Hz, 12 H), 7.87 (d, 3JH,H = 8.5 Hz, 12 H), 7.76 – 7.60 (m, 48 H), 7.55 – 7.46 (m, 12 H), 7.16 (d, 3JH,H = 8.0 Hz, 12 H), 7.03 (s, 6 H), 7.02 (s, 6 H), 6.96 (s, 12 H), 6.93 (s, 12 H), 6.86 (d, 3JH,H = 8.1 Hz, 12 H), 4.10 – 3.99 (m, 48 H), 3.99 – 3.90 (m, 24 H), 2.42 (t, 3JH,H = 7.0 Hz, 24 H), 1.95 – 1.72 (m, 96 H), 1.62 – 1.16 (m, 360 H), 1.15 – 0.97 (m, 168 H), 0.97 – 0.76 (m, 132 H); 1H NMR (500 MHz, CD2Cl2, 298 K) δ [ppm] = 8.14 (d, 3JH,H = 8.1 Hz, 12 H), 7.92 (d, 3JH,H = 8.5 Hz, 12 H), 7.79 – 7.66 (m, 36 H), 7.64 (s, 12 H), 7.54 – 7.44 (m, 12 H), 7.20 (d, 3JH,H = 8.2 Hz, 12 H), 7.05 (s, 6 H), 7.02 (s, 6 H), 6.99 (s, 12 H), 6.97 – 6.93 (m, 24 H), 4.08 – 3.98 (m, 48 H), 3.98 – 3.92 (m, 24 H), 2.41 (t, 3JH,H = 7.0 Hz, 24 H), 1.96 – 1.71 (m, 96 H), 1.65 – 1.17 (m, 360 H), 1.17 – 0.99 (m, 168 H), 0.99 – 0.76 (m, 132 H); 13C NMR (126 MHz, CDCl3, 298 K) δ [ppm] = 154.78, 154.06, 153.94, 153.79, 141.60, 140.49, 140.41, 140.10, 136.79, 132.63, 131.73, 130.90, 128.94, 127.99, 127.36, 124.58, 123.55, 123.50, 121.54, 121.26, 120.86, 120.21, 118.04, 117.40, 117.28, 116.51, 114.96, 114.65, 114.07, 113.58, 113.47, 104.31, 96.51, 95.56, 94.91, 87.61, 86.62, 70.16, 70.04, 70.00, 69.56, 32.27, 32.25, 32.24, 32.18, 29.82, 29.79, 29.75, 29.73, 29.71, 29.68, 26.52, 26.42, 26.40, 23.14, 23.13, 23.09, 23.08, 21.70, 21.17, 18.65, 18.41, 14.63, 14.57, 14.52, 14.50, 12.20, 10.04; 13C NMR (126 MHz, CD2Cl2, 298 K) δ [ppm] = 154.88, 154.20, 154.11, 153.93, 141.87, 140.89, 140.63, 140.50, 140.40, 136.88, 132.68, 132.04, 130.83, 129.11, 128.15, 127.61, 124.49, 123.69, 123.50, 121.66, 121.44, 121.10, 120.32, 117.99, 117.47, 117.28, 116.70, 114.90, 114.62, 114.20, 113.84, 113.62, 104.31, 96.45, 95.91, 95.35, 94.94, 87.71, 86.85, 86.80, 70.22, 70.14, 69.82, 32.44, 32.35, 29.97, 29.93, 29.90, 29.88, 29.83, 29.83, 26.69, 26.67, 26.58, 26.54, 23.31, 23.29, 23.25, 23.24, 21.89, 21.22, 18.56, 18.32, 14.57, 14.50, 14.45, 14.43, 12.35, 10.14;MS (MALDI-TOF, DCTB) (calcd. for C774H996N18O36Si12 monoisotopic: 11455.39, distr. max.: 11465.32): m/z11965.9 [M+2*DCTB]+, 11716.6 [M+DCTB]+, 11465.3 [M]+, 5856.8 [M+DCTB]2+, 5733.5 [M]2+; GPC (in THF vs. PS): Mp = 11580 g mol-1.

Soheil Zabihi
 http://www.nature.com/nchem/journal/v5/n11/compound/nchem.1758_comp7.html
http://www.nature.com/nchem/journal/v5/n11/extref/nchem.1758-s1.pdf
http://www.nature.com/nchem/journal/v5/n11/extref/nchem.1758-s1.pdf

Affiliations

  1. Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn, Germany

    • A. Vikas Aggarwal,
    • Alissa Idelson,
    • Daniel Kalle,
    • Stefan-S. Jester &
    • Sigurd Höger

  2. Department of Physics and Astronomy, University of Utah, Salt Lake City, Utah 84112, USA

    • Alexander Thiessen &
    • John M. Lupton

  3. Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstrasse 31, D-93040 Regensburg, Germany

    • Dominik Würsch,
    • Thomas Stangl,
    • Florian Steiner,
    • Jan Vogelsang &
    • John M. Lupton
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SMILES: CCCCCCCCOC(C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C1)=C1C#CC2=CC3=C(C=C2)C4=C(C=C(C#CC5=C(OCCCCCCCC)C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C5)C=C4)N3C(C=C6)=CC=C6C(C=C7)=CC=C7C#CC(C=C8OCCCCCCCC)=C(OCCCCCCCC)C=C8C#CC(C=C9)=CC=C9C%10=C(C%11=CC=C(C#CC%12=C(OCCCCCCCC)C=C(C#CC%13=CC=C(C%14=CC=C(N%15C(C=C(C#CC%16=CC(OCCCCCCCC)=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C=C%16OCCCCCCCC)C=C%17)=C%17C%18=C%15C=C(C#CC%19=CC(OCCCCCCCC)=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C=C%19OCCCCCCCC)C=C%18)C=C%14)C=C%13)C(OCCCCCCCC)=C%12)C=C%11)C(C%20=CC=C(C#CC%21=C(OCCCCCCCC)C=C(C#CC%22=CC=C(C%23=CC=C(N%24C(C=C(C#CC%25=C(OCCCCCCCC)C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C%25)C=C%26)=C%26C%27=C%24C=C(C#CC%28=C(OCCCCCCCC)C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C%28)C=C%27)C=C%23)C=C%22)C(OCCCCCCCC)=C%21)C=C%20)=C(C%29=CC=C(C#CC%30=CC(OCCCCCCCC)=C(C#CC%31=CC=C(C%32=CC=C(N%33C(C=C(C#CC%34=C(OCCCCCCCC)C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C%34)C=C%35)=C%35C%36=C%33C=C(C#CC%37=C(OCCCCCCCC)C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C%37)C=C%36)C=C%32)C=C%31)C=C%30OCCCCCCCC)C=C%29)C(C%38=CC=C(C#CC%39=C(OCCCCCCCC)C=C(C#CC%40=CC=C(C%41=CC=C(N%42C(C=C(C#CC%43=CC(OCCCCCCCC)=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C=C%43OCCCCCCCC)C=C%44)=C%44C%45=C%42C=C(C#CC%46=CC(OCCCCCCCC)=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C=C%46OCCCCCCCC)C=C%45)C=C%41)C=C%40)C(OCCCCCCCC)=C%39)C=C%38)=C%10C%47=CC=C(C#CC%48=C(OCCCCCCCC)C=C(C#CC%49=CC=C(C%50=CC=C(N%51C(C=C(C#CC%52=C(OCCCCCCCC)C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C%52)C=C%53)=C%53C%54=C%51C=C(C#CC%55=CC(OCCCCCCCC)=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C=C%55OCCCCCCCC)C=C%54)C=C%50)C=C%49)C(OCCCCCCCC)=C%48)C=C%47
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