Atropselective Dibrominations of a 1,1'-Disubstituted 2,2'-Biindolyl with Diverging Point-to-Axial Asymmetric Inductions. Deriving 2,2'-Biindolyl-3,3'-diphosphane Ligands for Asymmetric Catalysis
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim..
On the 1 H NMR timescale, 2,2'-biindolyls with (R)-configured (1-alkoxyprop)-2-yl, (1-hydroxyprop)-2-yl, or (1-siloxyprop)-2-yl substituents at C-1 and C-1' are atropisomerically stable at <0 °C and interconvert at >30 °C. A 2,2'-biindolyl (R,R)-17 a of that kind and achiral (!) brominating reagents gave the atropisomerically stable 3,3'-dibromobiindolyls (M)- and/or (P)-18 a at best atropselectively-because of point-to-axial asymmetric inductions-and atropdivergently, exhibiting up to 95 % (M)- and as much (P)-atropselectivity. This route to atropisomerically pure biaryls is novel and should extend to other substrates and/or different functionalizations. The dibromobiindolyls (M)- and (P)-18 a furnished the biindolyldiphosphanes (M)- and (P)-14 without atropisomerization. These syntheses did not require the resolution of a racemic mixture, which distinguishes them from virtually all biaryldiphosphane syntheses known to date. (M)- and (P)-14 acted as ligands in catalytic asymmetric allylations and hydrogenations. Remarkably, the β-ketoester rac-25 c was hydrogenated trans-selectively with 98 % ee; this included a dynamic kinetic resolution.
| Medienart: |
E-Artikel |
|---|
| Erscheinungsjahr: |
2019 |
|---|---|
| Erschienen: |
2019 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:58 |
|---|---|
| Enthalten in: |
Angewandte Chemie (International ed. in English) - 58(2019), 14 vom: 26. März, Seite 4714-4719 |
| Sprache: |
Englisch |
|---|
| Beteiligte Personen: |
Baumann, Thomas [VerfasserIn] |
|---|
| Links: |
|---|
| Themen: |
Asymmetric allylation |
|---|
| Anmerkungen: |
Date Completed 06.04.2020 Date Revised 08.04.2020 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
|---|
| doi: |
10.1002/anie.201806294 |
|---|
| funding: |
|
|---|---|
| Förderinstitution / Projekttitel: |
|
| PPN (Katalog-ID): |
NLM292767323 |
|---|
| LEADER | 01000naa a22002652 4500 | ||
|---|---|---|---|
| 001 | NLM292767323 | ||
| 003 | DE-627 | ||
| 005 | 20231225073836.0 | ||
| 007 | cr uuu---uuuuu | ||
| 008 | 231225s2019 xx |||||o 00| ||eng c | ||
| 024 | 7 | |a 10.1002/anie.201806294 |2 doi | |
| 028 | 5 | 2 | |a pubmed24n0975.xml |
| 035 | |a (DE-627)NLM292767323 | ||
| 035 | |a (NLM)30648782 | ||
| 040 | |a DE-627 |b ger |c DE-627 |e rakwb | ||
| 041 | |a eng | ||
| 100 | 1 | |a Baumann, Thomas |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Atropselective Dibrominations of a 1,1'-Disubstituted 2,2'-Biindolyl with Diverging Point-to-Axial Asymmetric Inductions. Deriving 2,2'-Biindolyl-3,3'-diphosphane Ligands for Asymmetric Catalysis |
| 264 | 1 | |c 2019 | |
| 336 | |a Text |b txt |2 rdacontent | ||
| 337 | |a ƒaComputermedien |b c |2 rdamedia | ||
| 338 | |a ƒa Online-Ressource |b cr |2 rdacarrier | ||
| 500 | |a Date Completed 06.04.2020 | ||
| 500 | |a Date Revised 08.04.2020 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. | ||
| 520 | |a On the 1 H NMR timescale, 2,2'-biindolyls with (R)-configured (1-alkoxyprop)-2-yl, (1-hydroxyprop)-2-yl, or (1-siloxyprop)-2-yl substituents at C-1 and C-1' are atropisomerically stable at <0 °C and interconvert at >30 °C. A 2,2'-biindolyl (R,R)-17 a of that kind and achiral (!) brominating reagents gave the atropisomerically stable 3,3'-dibromobiindolyls (M)- and/or (P)-18 a at best atropselectively-because of point-to-axial asymmetric inductions-and atropdivergently, exhibiting up to 95 % (M)- and as much (P)-atropselectivity. This route to atropisomerically pure biaryls is novel and should extend to other substrates and/or different functionalizations. The dibromobiindolyls (M)- and (P)-18 a furnished the biindolyldiphosphanes (M)- and (P)-14 without atropisomerization. These syntheses did not require the resolution of a racemic mixture, which distinguishes them from virtually all biaryldiphosphane syntheses known to date. (M)- and (P)-14 acted as ligands in catalytic asymmetric allylations and hydrogenations. Remarkably, the β-ketoester rac-25 c was hydrogenated trans-selectively with 98 % ee; this included a dynamic kinetic resolution | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a asymmetric allylation | |
| 650 | 4 | |a asymmetric hydrogenation | |
| 650 | 4 | |a atropselectivity | |
| 650 | 4 | |a biaryls | |
| 650 | 4 | |a bromination | |
| 700 | 1 | |a Brückner, Reinhard |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t Angewandte Chemie (International ed. in English) |d 1964 |g 58(2019), 14 vom: 26. März, Seite 4714-4719 |w (DE-627)NLM000105422 |x 1521-3773 |7 nnns |
| 773 | 1 | 8 | |g volume:58 |g year:2019 |g number:14 |g day:26 |g month:03 |g pages:4714-4719 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1002/anie.201806294 |3 Volltext |
| 912 | |a GBV_USEFLAG_A | ||
| 912 | |a GBV_NLM | ||
| 951 | |a AR | ||
| 952 | |d 58 |j 2019 |e 14 |b 26 |c 03 |h 4714-4719 | ||