2003
DOI: 10.3998/ark.5550190.0004.723
|View full text |Cite
|
Sign up to set email alerts
|

Total synthesis of cis, cis-ceratospongamide

Abstract: A total synthesis of cis, cis-ceratospongamide 1 was accomplished via 4+3 fragment condensation, macrolactamization and subsequent cyclodehydration. Macrolactamization of both linear peptides 4a & 4b produced the corresponding cyclopeptide 3 as a mixture of two conformational isomers (cis, cis 3a and cis, trans 3b). Further oxazoline ring closure furnished the cis, cis-ceratospongamide 1 which is identical to the natural product.

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
1

Citation Types

0
3
0

Year Published

2005
2005
2021
2021

Publication Types

Select...
5
2
1

Relationship

2
6

Authors

Journals

citations
Cited by 23 publications
(3 citation statements)
references
References 10 publications
0
3
0
Order By: Relevance
“…The low supply of rhizopodin, together with its interesting biological activity and intriguing structure, makes it an attractive target for total synthesis. As part of our research program directed toward the total synthesis, stereochemical and structural studies, and biological evaluation of natural products, we have embarked on the synthesis of rhizopodin. Herein we report a highly stereocontrolled synthesis of fragment 3 , corresponding to the C9−C23 (C9′−C23′) fragment of the natural product.…”
mentioning
confidence: 99%
“…The low supply of rhizopodin, together with its interesting biological activity and intriguing structure, makes it an attractive target for total synthesis. As part of our research program directed toward the total synthesis, stereochemical and structural studies, and biological evaluation of natural products, we have embarked on the synthesis of rhizopodin. Herein we report a highly stereocontrolled synthesis of fragment 3 , corresponding to the C9−C23 (C9′−C23′) fragment of the natural product.…”
mentioning
confidence: 99%
“…Synthesis of cis,cis -ceratospongamide ( 274 ) was also achieved by Chen, Deng, and Ye, who adopted [4 + 3] fragment condensation, macrolactamization, and subsequent cyclodehydration, shown in Scheme . Both the linear peptides 283 and 292 were prepared from Phe-Pro-thiazole and Phe-Pro-Ile- a Thr derivatives.…”
Section: Cyclic Peptides From Red Algamentioning
confidence: 99%
“…(S)-tert-Butyl 2-((S)-1-(methoxycarbonyl)-2-phenylethylcarbamoyl)pyrrolidine-1-carboxylate (4a) Yellow oil, yield 73 %, [α] 20 D = −38.7 (c = 1.24, CHCl 3 ); 45 1 H NMR (CDCl 3 , 500 MHz) δ 1.42 (bs, 9H, C(CH 3 ) 3 ), 1.77-1.86 (m, 2H, pro-γ), 1.88-2.06 (m, 2H, pro-β), 2.90-3.03 (m, 1H, PhCH 2 ), 3.19 (dd, J = 14.0, 5.5 Hz, 1H, PhCH 2 ), 3.29-3.39 (m, 2H, pro-δ), 3.72 (s, 3H, OCH 3 ), 4.19-4.29 (m, 1H, pro-α), 4.85 (bs, 1H, Phe-CH), 7.09 (bd, J = 7.0 Hz, 2H, ArH), 7.22-7.25 (m, 3H, ArH) ppm; 13 C NMR (CD 3 OD, 125 MHz) δ 24.3 (pro-γ), 28.5 (3 × CH 3 ), 32.2 (pro-β), 38.1 (PhCH 2 ), 47.8 (pro-δ), 52.7 (Phe-CH), 55.1 (OCH 3 ), 61.6 (pro-α), 81.5 (OC(CH 3 ) 3 ), 127.9 (C aro H), 129.5 (C aro H), 130.1 (C aro H), 138.3 (C aro ), 173.3 (C=O), 175.1 (C=O), 175.8 (C=O) ppm; FTIR (ATR) ν 3277, 3079, 3028, 2976, 2877, 1738, 1689, 1660, 1552, 1445, 1389, 1365, 1210 cm -1 . (S)-tert-Butyl 2-(((S)-3-hydroxy-1-methoxy-1-oxopropane-2-yl)carbamoyl)-pyrrolidine-1-carboxylate (4c)Colorless oil, yield 94 %, [α] 20 D = +88.0 (c = 1.00, CH 3 OH);46 1 H NMR (CD 3 OD, 500 MHz) δ 1.45 and 1.48 (s, 9H, 3 × CH 3 , rotamers), 1.88-1.92 (m, 1H, pro-γ), 1.94-1.98 (m, 1H, pro-γ), 2.00-2.05 (m, 1H, pro-β), 2.12-2.29 (m, 1H, pro-β), 3.33 (brs, 1H, OH), 3.40-3.45 (m, 1H, pro-δ), 3.51-3.55 (m, 1H, pro-δ), 3.74 (s, 3H, OCH 3 ), 3.79-3.85 (m, 1H, CH 2 OH), 3.91-3.96 (m, 1H, CH 2 OH), 4.27-4.30 (m, 1H, pro-α), 4.53-4.55 (m, 1H, CHCH 2 OH) ppm; FTIR (ATR) ν 3293, 3082, 2975, 2881, 1743, 1662, 1533, 1470, 1454, 1205, 1160 cm -1 . (S)-2-((S)-tert-Butyl 2-carbamoylpyrrolidine-1-carboxyloyl)-3-phenyl-propanoic acid (5a)White solid, yield 96 %, mp 143−144 °C (mp 145-147 °C)45,47 ; [α] 20 D = −43.1 (c= 1.3, CHCl 3 ).…”
mentioning
confidence: 99%