Abstract
Synthesis of (S)-3-mercapto-1-heptyl acetate was achieved in four steps. Sharpless asymmetric epoxidation of (E)-2-heptenol yielded (2R,3R)-2,3-epoxy-1-heptanol, which was treated with thiourea in the presence of Ti(OPri)4 to give (2S,3S)-2,3-epithio-1-heptanol, reduction of which followed by acetylation afforded (S)-3-mercapto-1-heptyl acetate in 91% ee. The optically active product possessed a tropical fruit aroma reminiscent of mango and passion fruit, with berry, ester-like, sweet, and pepper-like aspects.
References
1.
Buttery R.G.
,
Teranishi R.
,
Ling L.C.
, and
Turnbaugh J.G.
, J. Agric. Food Chem. , 1990 , 38 , 336 .
2.
Boelens M.H.
, and
van Gemert L.J.
, Perfum. Flavour. , 1993 , 18 , 29 .
3.
Simian H.
,
Robert F.
, and
Blank I.
, J. Agric. Food Chem. , 2004 , 52 , 306 .
4.
Naef R.
,
Velluz A.
, and
Jaquier A.
, J. Agric. Food Chem. , 2008 , 56 , 517 .
5.
Starkenmann C.
, and
Niclass Y.
, J. Agric. Food Chem. , 2011 , 59 , 3358 .
6.
Widder S.
,
Sabater Lüntzel C.
,
Dittner T.
, and
Pickenhagen W.
, J. Agric. Food Chem. , 2000 , 48 , 418 .
7.
Vermeulen C.
, and
Collin S.
, J. Agric. Food Chem. , 2002 , 50 , 5654 .
8.
Vermeulen C.
, and
Collin S.
, J. Agric. Food Chem. , 2003 , 51 , 3618 .
9.
Bailly S.
,
Jerkovic V.
,
Marchand-Brynaert J.
, and
Collin S.
, J. Agric. Food Chem. , 2006 , 54 , 7227 .
10.
Gros J.
,
Nizet S.
, and
Collin S.
, J. Agric. Food Chem. , 2011 , 59 , 8853 .
11.
Gros J.
,
Peeters F.
, and
Collin S.
, J. Agric. Food Chem. , 2012 , 60 , 7805 .
12.
van de Waal M.
,
Niclass Y.
,
Snowden R.L.
,
Bernardinelli G.
, and
Escher S.
, Helv. Chim. Acta , 2001 , 84 , 1246 .
13.
Nörenberg S.
,
Reichardt B.
,
Andelfinger V.
,
Eisenreich W.
, and
Engel K.-H.
, J. Agric. Food Chem. , 2013 , 61 , 2062 .
14.
Escher S.
,
Niclass Y.
,
van de Waal M.
, and
Starkenmann C.
, Chem. Biodiver. , 2006 , 3 , 943 .
15.
Waddell W.J.
,
Cohen S.M.
,
Feron V.J.
,
Goodman J.I.
,
Marnett L.J.
,
Portoghese P.S.
,
Reitjiens I.M.C.M.
,
Smith R.L.
,
Adams T.B.
,
Lucas Gavin C.
,
McGowen M.M.
, and
Williams M.C.
, Food Technol. , 2007 , 61 , 22 .
16.
Escher S.D.
,
Niclass Y.
, and
Saudan L.
, WO 2006/120625.
17.
Utaka M.
,
Watabu H.
,
Higashi H.
,
Sakai T.
,
Tsuboi S.
, and
Torii S.
, J. Org. Chem. , 1990 , 55 , 3917 .
18.
Oppolzer W.
, and
Starkemann C.
, Tetrahedron Lett. , 1992 , 33 , 2439 .
19.
Katsuki T.
, and
Sharpless K.B.
, J. Am. Chem. Soc. , 1980 , 102 , 5974 .
20.
Pickenhagen W.
, and
Brönner-Schindler H.
, Helv. Chim. Acta , 1984 , 67 , 947 .
21.
Gao Y.
, and
Sharpless K.B.
, J. Org. Chem. , 1988 , 53 , 4114 .
22.
Karlsson S.
, and
Hogberg H.-E.
, Org. Lett. , 1999 , 1 , 1667 .
23.
El-Batta A.
,
Jiang C.
,
Zhao W.
,
Anness R.
,
Cooksy A.L.
, and
Bergdahl M.
, J. Org. Chem. , 2007 , 72 , 5244 .
24.
Shekhar V.
,
Reddy D.K.
, and
Venkateswarlu Y.
, Helv. Chim. Acta , 2012 , 95 , 1593 .
25.
Pereira C.L.
,
Chen Y.-H.
, and
McDonald F.E.
, J. Am. Chem. Soc. , 2009 , 131 , 6066 .
26.
Tian H.
,
Sun B.
,
Tang L.
, and
Ye H.
, Flavour Frag. J. , 2011 , 26 , 65 .
27.
Apfel C.
,
Banner D.W.
,
Bur D.
,
Dietz M.
,
Hirata T.
,
Hubschwerlen C.
,
Locher H.
,
Page M.G.P.
,
Pirson W.
,
Rossé G.
, and
Specklin J.-L.
, J. Med. Chem. , 2000 , 43 , 2324 .