Synthesis-guided structure revision of the sarcodonin, sarcoviolin, and hydnellin natural product family.
A sweeping structural revision of the sarcodonin natural product family (published structures 1a-13a) is proposed after extensive studies aimed at their chemical synthesis. Key features of revised structure 1b include replacement of the N,N-dioxide moiety with an oxime, ring-opening of the central diketopiperazine, and transposition of the terphenyl wing from the 1β-2β position of 1a to the 2β-3β position of 1b. This structure revision arose from the serendipitous synthesis of a benzodioxane aminal (44) whose structure was unambiguously determined by X-ray crystallography and whose spectral properties bore considerable resemblance to the published data for the sarcodonins. A versatile new method for O-arylation of hydroxamic acids is also reported herein, as well as a manganese(III)-mediated α-oxidation of hydroxamic acids to aminals.
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
David W
DW
Lin
Takeshi
T
Masuda
Moritz B
MB
Biskup
Jonathan D
JD
Nelson
Phil S
PS
Baran
D001688:Biological Products / Q000737:chemistry*; D018360:Crystallography, X-Ray; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013729:Terpenes / Q000737:chemistry*
D001688:Biological Products; D013729:Terpenes; C571786:hydnellin; C117589:sarcodonin M; C571785:sarcoviolin
Org Lett. 2003 Dec 11;5(25):4907-9
14653704
Nat Prod Rep. 2009 Sep;26(9):1105-24
19693411
Angew Chem Int Ed Engl. 1998 Aug 17;37(15):2046-2067
29711045
Chem Rev. 1996 Feb 1;96(1):339-364
11848756
Mar Drugs. 2009 Jul 13;7(3):314-30
19841716
J Am Chem Soc. 2006 Feb 15;128(6):1810-1
16464078
Org Lett. 2005 Jan 20;7(2):179-82
15646952
J Am Chem Soc. 2004 Jul 14;126(27):8396-8
15237994
J Am Chem Soc. 2002 Jul 10;124(27):7904-5
12095326
Chem Rev. 2003 Oct;103(10):4131-46
14531720
J Am Chem Soc. 2006 Mar 8;128(9):2859-72
16506764
Chem Pharm Bull (Tokyo). 2006 Jun;54(6):912-4
16755070
Org Lett. 2007 Oct 11;9(21):4131-4
17850091
Angew Chem Int Ed Engl. 2008;47(35):6579-82
18651685
J Med Chem. 2005 Mar 10;48(5):1576-87
15743199
Molecules. 2005 Jan 31;10(1):190-4
18007286
Angew Chem Int Ed Engl. 2007;46(13):2320-4
17318930
Bioorg Med Chem. 2004 Jun 1;12(11):3079-96
15142567
J Am Chem Soc. 2006 Feb 22;128(7):2244-57
16478178
J Org Chem. 2006 Apr 14;71(8):3176-83
16599616
Angew Chem Int Ed Engl. 2007;46(35):6586-94
17724780
J Nat Prod. 2000 Mar;63(3):347-51
10757716
J Am Chem Soc. 2006 Feb 22;128(7):2258-67
16478179
Org Lett. 2008 Jul 17;10(14):3005-8
18557628
Bioorg Med Chem. 2006 Aug 15;14(16):5711-20
16650996
Angew Chem Int Ed Engl. 2005 Feb 4;44(7):1012-1044
15688428
Angew Chem Int Ed Engl. 2010 Feb 1;49(6):1095-8
20041464
J Am Chem Soc. 2010 Feb 24;132(7):2157-9
20108904
J Am Chem Soc. 2007 Oct 24;129(42):12896-900
17902668
Org Lett. 2007 Nov 22;9(24):4955-8
17958435
Org Lett. 2001 Jan 11;3(1):139-42
11429858
Org Lett. 2008 Dec 4;10(23):5493-6
19006315
J Am Chem Soc. 2010 May 26;132(20):7153-76
20443558
Nat Prod Res. 2003 Aug;17(4):293-9
12822910
J Am Chem Soc. 2010 May 26;132(20):7138-52
20443561
Org Biomol Chem. 2009 Jan 21;7(2):238-52
19109668
Science. 2009 Apr 10;324(5924):238-41
19359584
Angew Chem Int Ed Engl. 2006 Nov 6;45(43):7199-202
17024712
J Chem Soc Perkin 1. 1975;(23):2511-3
1239456
Chem Pharm Bull (Tokyo). 1962 Jan;10:51-4
13952269
Angew Chem Int Ed Engl. 2003 Nov 17;42(44):5400-49
14618572
Org Biomol Chem. 2003 Jan 21;1(2):373-80
12929433
J Org Chem. 2005 Dec 9;70(25):10271-84
16323835
Chem Pharm Bull (Tokyo). 1964 Jan;12:125-6
14185745
Nat Prod Rep. 1989 Apr;6(2):111-41
2664583
J Org Chem. 2010 Nov 19;75(22):7757-68
21028907
J Org Chem. 2000 Oct 20;65(21):6922-31
11031011
J Org Chem. 1998 Aug 21;63(17):5831-5837
11672184
J Org Chem. 2002 Jul 12;67(14):4635-9
12098269