Asymmetric Total Synthesis of (+)-Inthomycin C via O-Directed Free Radical Alkyne Hydrostannation with Ph3SnH and Catalytic Et3B: Reinstatement of the Zeeck-Taylor (3R)-Structure for (+)-Inthomycin C

被引：38

作者：

Hale, Karl J. ^{[1
]}

Grabski, Milosz

Manaviazar, Soraya

Maczka, Maciej

机构：

[1] Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 5AG, Antrim, North Ireland

来源：

ORGANIC LETTERS | 2014年 / 16卷 / 04期

关键词：

ENANTIOSELECTIVE SYNTHESIS; TERMINAL ALKYNES; ALDEHYDES; ION; DIHYDROXYLATION; PHTHOXAZOLIN; ALCOHOLS; NMR;

D O I：

10.1021/ol5000499

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A new pathway to (+)-inthomycin C is reported that exploits an O-directed free radical hydrostannation reaction on (-)-12 and a Stille cross-coupling as key steps. Significantly, the latter process was effected on 19 where a gauche-pentane repulsive interaction could interfere. Our stereochemical studies on the alkynol (-)-12 and the enyne (+)-7 confirm that Ryu and Hatakeyama's (3S)-stereochemical revision of (+)-inthomycin C is invalid and that Zeeck and Taylor's original (3R)-stereostructure for (+)-inthomycin C is correct.

引用

页码：1164 / 1167

页数：4

共 25 条

[1] Selective dihydroxylation of non-conjugated dienes in favor of the terminal olefin [J].

Andrus, MB ;

Lepore, SD ;

Sclafani, JA .

TETRAHEDRON LETTERS, 1997, 38 (23) :4043-4046

[2] ACUTIPHYCIN AND 20,21-DIDEHYDROACUTIPHYCIN, NEW ANTINEOPLASTIC AGENTS FROM THE CYANOPHYTE OSCILLATORIA-ACUTISSIMA [J].

BARCHI, JJ ;

MOORE, RE ;

PATTERSON, GML .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (26) :8193-8197

[3] Efficient enantioselective additions of terminal alkynes and aldehydes under operationally convenient conditions [J].

Boyall, D ;

Frantz, DE ;

Carreira, EM .

ORGANIC LETTERS, 2002, 4 (15) :2605-2606

[4] Enantioselective addition of 2-methyl-3-butyn-2-ol to aldehydes:: Preparation of 3-hydroxy-1-butynes [J].

Boyall, D ;

López, F ;

Sasaki, H ;

Frantz, D ;

Carreira, EM .

ORGANIC LETTERS, 2000, 2 (26) :4233-4236

[5] NUCLEAR MAGNETIC-RESONANCE ENANTIOMER REAGENTS - CONFIGURATIONAL CORRELATIONS VIA NUCLEAR MAGNETIC-RESONANCE CHEMICAL-SHIFTS OF DIASTEREOMERIC MANDELATE, O-METHYLMANDELATE, AND ALPHA-METHOXY-ALPHA-TRIFLUOROMETHYLPHENYLACETATE (MTPA) ESTERS [J].

DALE, JA ;

MOSHER, HS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (02) :512-519

[6] Mechanistic studies on the O-directed free-radical hydrostannation of disubstituted acetylenes with Ph3SnH and Et3B and on the iodination of allylically oxygenated α-triphenylstannylalkenes [J].

Dimopoulos, P ;

George, J ;

Tocher, DA ;

Manaviazar, S ;

Hale, KJ .

ORGANIC LETTERS, 2005, 7 (24) :5377-5380

[7] O-directed free-radical hydrostannations of propargyl ethers, acetals, and alcohols with Ph3SnH and Et3B [J].

Dimopoulos, P ;

Athlan, A ;

Manaviazar, S ;

George, J ;

Walters, M ;

Lazarides, L ;

Aliev, AE ;

Hale, KJ .

ORGANIC LETTERS, 2005, 7 (24) :5369-5372

[8] On the stereospecific conversion of proximally-oxygenated trisubstituted vinyltriphenylstannanes into stereodefined trisubstituted alkenes [J].

Dimopoulos, P ;

Athlan, A ;

Manaviazar, S ;

Hale, KJ .

ORGANIC LETTERS, 2005, 7 (24) :5373-5376

[9] Facile enantioselective synthesis of propargylic alcohols by direct addition of terminal alkynes to aldehydes [J].

Frantz, DE ;

Fässler, R ;

Carreira, EM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (08) :1806-1807

[10] Cuprous chloride accelerated Stille reactions. A general and effective coupling system for sterically congested substrates and for enantioselective synthesis [J].

Han, XJ ;

Stoltz, BM ;

Corey, EJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (33) :7600-7605

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