Phenylsilane → HCID 117736344, compound

HRID 1482297Notes

Reaction equation

C1([SiH3])C=CC=CC=1.[C:8]([S:12][S:13][CH2:14][C@H:15]([NH:111]C(=O)OCC=C)[C:16](=[O:110])[NH:17][CH2:18][CH2:19][CH2:20][CH2:21][C@H:22]1[C:54](=[O:55])[NH:53][C@@H:52]([CH2:56][CH:57]([CH3:59])[CH3:58])[C:51](=[O:60])[N:50]([CH3:61])[C@@H:49]([CH3:62])[C:48](=[O:63])[N:47]([CH3:64])[C@@H:46]([CH2:65][CH:66]([CH3:68])[CH3:67])[C:45](=[O:69])[NH:44][C@@H:43]([CH3:70])[C:42](=[O:71])[N:41]([CH3:72])[C@@H:40]([CH2:73][C:74]2[CH:79]=[CH:78][CH:77]=[CH:76][CH:75]=2)[C:39](=[O:80])[N:38]([CH3:81])[C@@H:37]([CH3:82])[C:36](=[O:83])[NH:35][C@@H:34]([CH3:84])[C:33](=[O:85])[NH:32][C@@H:31]([CH2:86][C:87]2[CH:92]=[CH:91][CH:90]=[CH:89][CH:88]=2)[C:30](=[O:93])[O:29][CH:28]([CH2:94][S:95][S:96][C:97]([CH3:100])([CH3:99])[CH3:98])[C:27](=[O:101])[NH:26][C@@H:25]([CH2:102][C:103]2[CH:108]=[CH:107][CH:106]=[CH:105][CH:104]=2)[C:24](=[O:109])[NH:23]1)([CH3:11])([CH3:10])[CH3:9]>CN1CCN(C)C1=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:111][C@@H:15]([CH2:14][S:13][S:12][C:8]([CH3:11])([CH3:10])[CH3:9])[C:16]([NH:17][CH2:18][CH2:19][CH2:20][CH2:21][C@H:22]1[C:54](=[O:55])[NH:53][C@@H:52]([CH2:56][CH:57]([CH3:59])[CH3:58])[C:51](=[O:60])[N:50]([CH3:61])[C@@H:49]([CH3:62])[C:48](=[O:63])[N:47]([CH3:64])[C@@H:46]([CH2:65][CH:66]([CH3:67])[CH3:68])[C:45](=[O:69])[NH:44][C@@H:43]([CH3:70])[C:42](=[O:71])[N:41]([CH3:72])[C@@H:40]([CH2:73][C:74]2[CH:75]=[CH:76][CH:77]=[CH:78][CH:79]=2)[C:39](=[O:80])[N:38]([CH3:81])[C@@H:37]([CH3:82])[C:36](=[O:83])[NH:35][C@@H:34]([CH3:84])[C:33](=[O:85])[NH:32][C@@H:31]([CH2:86][C:87]2[CH:88]=[CH:89][CH:90]=[CH:91][CH:92]=2)[C:30](=[O:93])[O:29][CH:28]([CH2:94][S:95][S:96][C:97]([CH3:98])([CH3:99])[CH3:100])[C:27](=[O:101])[NH:26][C@@H:25]([CH2:102][C:103]2[CH:104]=[CH:105][CH:106]=[CH:107][CH:108]=2)[C:24](=[O:109])[NH:23]1)=[O:110]

Participants

Conditions

Temperature: 30 °C

Procedure

A solution of phenylsilane (PhSiH3) (0.385 μl, 3.12 μmol) in 1,3-dimethyl-2-imidazolidinone (DMI) (140 μl), and tetrakis(triphenylphosphine)palladium (0) (Pd(Ph3P)4) (1.80 mg, 1.56 μmol) were added to allyl ((2R)-3-(tert-butyldisulfanyl)-1-oxo-1-((4-((5S,8S,11S,14S,17S,20S,23S,26S,29S,32S)-5,23,32-tribenzyl-2-((tert-butyldisulfanyl)methyl)-11,17-diisobutyl-13,14,16,20,22,25,26,29-octamethyl-3,6,9,12,15,18,21,24,27,30,33-undecaoxo-1-oxa-4,7,10,13,16,19,22,25,28,31-decaazacyclotritriacontan-8-yl)butyl)amino)propan-2-yl)carbamate (*Phe-tBuSSlac-Phe-Lys(Alloc-Cys(StBu))-Leu-MeAla-MeLeu-Ala-MePhe-MeAla-Ala*, cyclized at two * sites) (Compound SP671) (2.5 mg, 1.56 μmol) at room temperature, and the reaction solution was stirred at 30° C. for 1 hour and 30 minutes. The reaction solution was purified by reverse-phase silica gel chromatography (0.1% aqueous formic acid/0.1% formic acid-acetonitrile solution) to afford (2R)-2-amino-3-(tert-butyldisulfanyl)-N-(4-((5S,8S,11S,14S,17S,20S,23S,26S,29S,32S)-5,23,32-tribenzyl-2-((tert-butyldisulfanyl)methyl)-11,17-diisobutyl-13,14,16,20,22,25,26,29-octamethyl-3,6,9,12,15,18,21,24,27,30,33-undecaoxo-1-oxa-4,7,10,13,16,19,22,25,28,31-decaazacyclotritriacontan-8-yl)butyl)propanamide (*Phe-tBuSSlac-Phe-Lys(H-Cys(StBu))-Leu-MeAla-MeLeu-Ala-MePhe-MeAla-Ala*, cyclized at two * sites) (Compound SP665) (2.60 mg, 88%).

Workup

customThe reaction solution was purified by reverse-phase silica gel chromatography (0.1% aqueous formic acid/0.1% formic acid-acetonitrile solution)

Sources & evidence

ORD record: ord-cc9a741d90fe4460a6670d30abad732c
Source dataset: uspto-grants-2016_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09409952B2

Reaction notes

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