Practical enantioselective synthesis of fully deuterated (R)-mevalonolactone

Article abstract of DOI:10.1016/S0040-4020(03)00983-9

Practical enantioselective synthetic method of fully deuterated (R)-mevalonolactone has been developed based upon Sharpless asymmetric epoxidation. (R)-Mevalonolactone-d₉ 1 was prepared on multi-gram scale in seven steps in 17% overall yield.

Full text of DOI:10.1016/S0040-4020(03)00983-9

Tetrahedron 59 (2003) 6035–6038
Practical enantioselective synthesis of fully deuterated
(R)-mevalonolactone
a
b
Tadashi Eguchi,a Eriko Watanabe and Katsumi Kakinuma
,
*
aDepartment of Chemistry and Materials Science, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8551, Japan
bDepartment of Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8551, Japan
Received 4 June 2003; revised 23 June 2003; accepted 23 June 2003
Abstract—Practical enantioselective synthetic method of fully deuterated (R)-mevalonolactone has been developed based upon Sharpless
asymmetric epoxidation. (R)-Mevalonolactone-d9 1 was prepared on multi-gram scale in seven steps in 17% overall yield.
q 2003 Elsevier Ltd. All rights reserved.
1. Introduction
methodology may well be meritorious for mechanistic
enzymology, particularly, the key transformation involving
proton attack and/or proton quench in the studies of terpene
biosynthesis. In fact, by using this racemic perdeuterated
mevalonolactone-d9, straightforward stereochemical anal-
ysis of isoprenoid biosynthesis has recently been demon-
strated as well by labeling experiments and 1H NMR
spectroscopy.8 However, development of efficient synthetic
methodology for chiral version of fully deuterated mevalo-
nate is apparently desirable for these type of feeding
experiments on the view point of molecular economy. In
this paper, we describe an enantioselective and practical
synthesis of chiral mevalonolactone-d9 (1) on multi-gram
scale.
Isoprenoids are biosynthesized by consecutive conden-
sations of their five-carbon precursor, isopentenyl dipho-
sphate, to the isomeric starter, dimethylallyl diphosphate.
Two pathways for these precursors are known. One is the
so-called mevalonate pathway,1 which operates in eucary-
otes, archaea, and cytosols of higher plants. The other is a
recently discovered pathway, the non-mevalonate pathway,
which is used by eubacteria, green algae, and chloroplasts of
higher plants.2 (R)-Mevalonate is the essential and first
biosynthetic precursor in the mevalonate pathway to
varieties of isoprenoids such as various vertebrate- and
invertebrate hormones, membrane-anchors of proteins
including oncogene products, membrane core lipids of
archaea, visual pigments, vitamins and an enormous number
of terpenoids in microorganisms, plants and animals.3 Since
the isotope-tracer methodology is vital for diverse aspects of
research in this field, various isotopomers of racemic4 and
chiral5 mavalonate and mavalonolactone have been pre-
pared to date, and tritium and/or deuterium as tracers are
usually used for stereochemical analysis of terpenoid
biosynthesis. However, it is also conceivable that protium
can be utilized to track hydrogen when the background
protium can be significantly reduced.
2. Results and discussion
The enantioselective synthesis of fully deuterated mevalo-
nolactone was based on our previous synthesis of racemic
7
mevalonate-d9 as shown in Scheme 1. First, both of two
precursors, 3,4-dimethoxyphenylacetone-d5 27 and triethyl
phosphonoaceate-d2 39 were prepared by simple exchange
reaction of the non-deuterated counterparts with 2H2O in the
presence of K2CO3. Horner–Emmons reaction between the
deuterated precursor 2 and the deuterated phosphonoacetate
3, instead of previously employed methyl ester derivative,7
proceeded smoothly to give ester 4 as a mixture of
geometrical isomers (E/Z¼5.5). The geometry of the
deuterated a,b-unsaturated ester 4 was determined by
comparison of 1H and 13C NMR with non-labelled
compound. A crucial improvement was the use of ethyl
ester instead of methyl ester, thus, a geometrical ratio was
improved from E/Z¼3 to 5.5, and importantly the major E-
isomer was obtained in crystalline form. Thus, recrystalliza-
tion from hexane gave a pure E-isomer 4 in 59% yield. The
Along this line, we previously reported the enantioselective
synthesis of (R)-mevalonolactone-d9 using chirality control
on a carbohydrate template.6 However, synthetic efficiency
must be further improved for practical use. We recently
devised an easy and convenient method for the gram scale
synthesis of mevalonolactone-d9 in a racemic form.7 This
Keywords: mevalonate; synthesis; stable isotope; deuterium; labeling.
*
Corresponding author. Tel.: þ81-3-5734-2631; fax: þ81-3-5734-2631;
e-mail: eguchi@cms.titech.ac.jp
0040–4020/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0040-4020(03)00983-9

6036
T. Eguchi et al. / Tetrahedron 59 (2003) 6035–6038
conditions afforded the desired (R)-mevalonolactone-d9 1 in
17% overall yield in seven steps.
The structure of mevalonolactone-d9 was confirmed by
spectroscopic data and the absolute configuration was
confirmed by its optical rotation; [a]D¼220.5 (c 6.13,
ethanol), [lit., [a]D¼225.6,12a 223.7,12 222,13b 217.6,13c
221.6,13d 220,13e 223,13f 223.4,13g 223,13h 219.913i for
non-labelled compound]. The deuterium contents of the
synthesized 1 were estimated by 1H NMR to be 96, 99, 99,
and 97% at C-2, C-4, C-5, and the methyl group,
respectively. In summary, we have successfully developed
a multi-gram scale synthetic method for highly optically
active and fully deuterated (R)-mevalonolactone.
3. Experimental
3.1. General
2
Deuteriochloroform (99.8% atom H, Merck) was used as
1
the solvent for H and 13C NMR spectra, unless otherwise
stated. 1H, 2H, 19F and 13C NMR chemical shifts were
reported in d values based on internal TMS (dH 0), a solvent
signal (CHCl3: dD 7.26, CDCl3: dC 77.0) or external
CF3COOH (dF 277.0) as references. J values are given in
hertz. Elemental analyses were performed with a Perkin–
Elmer 2400 apparatus. Column chromatography was carried
out with Kieselgel 60 (63–200 mesh, Merck). All reactions
were carried out in an argon atmosphere. THF and ether
were distilled from sodium/benzophenone ketyl prior to use.
CH2Cl2 and pyridine were distilled from P2O5 and
potassium hydroxide, respectively. Deuterium oxide
(99.8% atom 2H) and LiAl2H4 (99% atom 2H) were
purchased from Merck and Isotec Inc., respectively.
Scheme 1. Synthesis of mevalonolactone-d9 1. (a) NaH, THF, then 2, and
then recrystallization, 59%. (b) LiAl2H4, ether, 74%. (c) TBHP, (L)-(þ)-
DIPT, Ti(OiPr)4, CH2Cl2, and then recrystallization, 77%. (d) LiAl2H4,
THF, 86%. (e) Ac2O, DMAP, Et3N, CH2Cl2, 99%. (f) RuCl3, NaIO4,
CCl4–CH3CN–H2O, 71%. (g) K2CO3–MeOH, and then H3Oþ, 86%.
3.1.1. Triethyl phosphono[2,2-2H2]acetate (3). To a
mixture of triethyl phosphonoacetate (60.0 g, 268 mmol)
and deuterium oxide (17.3 g, 865 mmol), K2CO3 (1.08 g,
7.8 mmol) was added. The solution was stirred for 1.5 h at
room temperature and was extracted with CHCl3. The
extract was dried over MgSO4 and concentrated to dryness.
This procedure was repeated five times to give 3 (56.9 g,
quant.). 1H NMR (270 MHz): d 1.29 (t, J¼7.2 Hz, 3H), 1.35
(t, J¼7.0 Hz, 6H), 4.18 (dq, J¼8.1, 7.0 Hz, 4H), 4.20 (q,
J¼7.2 Hz, 2H); 13C NMR (75 MHz): d 13.60, 15.84, 33.59
(double quintet, J¼132.8, 19.2 Hz), 62.09, 62.17, 165.12.
3.1.2. Ethyl (E)-3-[2H3]methyl-4-(3,4-dimethoxyphenyl)-
[2,4,4-2H3]but-2-enoate (4). Tetrahydrofuran (350 ml) was
added to pre-washed sodium hydride (7.1 g, 178 mmol), and
then 3 (42.3 g, 187 mmol) was added portionwise at 08C. The
mixture was stirred for 1 h at room temperature. A solution of
2 (34.9 g, 175 mmol) in THF (160 ml) was then added at 08C.
The resulting mixture was stirred for 7 h at room temperature.
Then, acetic acid (7.5 ml) and water (20 ml) were added, and
the mixture was extracted four times with EtOAc. The
combined organic layer was washed with NaHCO3 aq and
brine, driedoverMgSO4, filtered, andconcentrated todryness.
The residue was purified by silica gel column chromatography
withhexane–EtOAc(5:1–1:1)togiveoilyester(41.8 g,89%)
as a geometrical mixture (E/Z¼ca. 5.5). Recrystallization of
the mixture from hexane gave a pure E-isomer 4 (27.8 g,
resulting E-ester 4 was subsequently reduced with LiAl2H4
to afford allylic alcohol 5 in 74% yield. Under these
reduction conditions, the saturated alcoholic product
derived from the 1,4-addition of deuteride and reduction
of the ester function was formed along with the desired
allylic alcohol.
The desired allylic alcohol 5 was next subjected to the
asymmetric Sharpless epoxidation10 with t-butyl hydroper-
oxide, (L)-(þ)-diisopropyl tartrate, and Ti(OiPr)4, in
CH2Cl2 to yield epoxide 6. The enantiomeric purity of the
epoxide 6 was determined to be 92% ee by 19F NMR
analysis of its (þ)-MTPA ester derivative (major isomer;
dF¼272.96, minor isomer dF¼273.04 in CDCl3-d6).
When (L)-(þ)-diethyl tartrate was used instead of (L)-(þ)-
diisopropyl tartrate, enantiomeric excess was as low as 80%.
Fortunately, the resulting expoxide 6 was obtained again in
crystalline form and the enatiomeric excess was further
improved to .99% ee by recrystallization from ethyl
acetate. Further reduction of 6 with LiAl2H4 easily afforded
the desired diol 7 in 86% yield. Two hydroxyl groups were
then protected as acetate 8 under standard conditions.
Ruthenium oxidation11 of 8 proceeded smoothly, and
carboxylic acid 9 was obtained in good yield; [a]D¼22.8
(c 0.97, ethanol), [lit., [a]D¼23.6 for non-labelled
compound].12 Deprotection and final extraction under acidic

T. Eguchi et al. / Tetrahedron 59 (2003) 6035–6038
6037
1
59%). Mp 47.2–49.08C; H NMR (270 MHz): d 1.27 (t,
3.1.5. (S)-5-(3,4-Dimethoxyphenyl)-3-[2H3]methyl-
[1,1,2,2,4,4-2H6]pentane-1,3-diol (7). To a suspension of
lithium aluminium deuteride (1.75 g, 41.7 mmol) in THF
(78 ml), a solution of 6 (9.33 g, 37.9 mmol) in THF (97 ml)
was added at 08C. The mixture was stirred at room
temperature for 2.5 h. Water (1.75 ml), 15% NaOH aq
(1.75 ml), and water (5.25 ml) were successively added at
08C. The insoluble matter was filtered and washed with
EtOAc. The filtrate and washings were combined, dried
over MgSO4, and concentrated to dryness. The residue was
purified by silica gel column chromatography with hexane–
EtOAc (1:1–1:2) to give 7 (8.63 g) as colorless solid.
Recrystallization of the solid from EtOAc gave crystalline 7
(8.29 g, 86%). Mp 91.8–93.08C; [a]2D7¼26.03 (c 1.09,
CHCl3); 1H NMR (300 MHz): d 2.56 (br, 1H), 3.06 (br, 1H),
3.87 (s, 6H), 6.72–6.83 (m, 3H); 13C NMR (75 MHz): d
25.36 (septet, J¼18.5 Hz), 40.30 (quintet, J¼19.1 Hz),
47.19 (quintet, J¼18.5 Hz), 55.52, 58.34 (quintet,
J¼21.6 Hz), 72.89, 110.62, 113.57, 122.29, 129.54,
J¼7.2 Hz, 3H), 3.86 (s, 3H), 3.87 (s, 3H), 4.15 (q, J¼7.2 Hz,
2H), 6.65–6.82 (m, 3H); 13C NMR (75 MHz): d 13.73, 17.07
(septet, J¼19.4 Hz), 45.17(quintet, J¼19.3 Hz), 55.17, 58.88,
110.69, 111.69, 116.09 (t, J¼23.3 Hz), 120.72, 129.58,
147.29, 148.43, 157.88, 165.94; IR (CHCl3): 1628,
1705 cm21. Anal. calcd for C15H142H6O4: C, 66.63; Hþ H,
2
2
7.45. Found: C, 66.78; Hþ H, 7.15.
3.1.3. (E)-5-(3,4-Dimethoxyphenyl)-3-[2H3]methyl-2-
[1,1,2,4,4-2H5]pent-2-en-1-ol (5). To a suspension of
lithium aluminum deuteride (2.75 g, 65.4 mmol) in ether
(212 ml), a solution of 4 (17.7 g, 65.4 mmol) in ether
(176 ml) was added at 08C. The mixture was stirred at 08C
for 2.5 h. Water (2.7 ml), 15% NaOH aq (2.7 ml), and water
(8.1 ml) were successively added at 08C. The insoluble
matter was filtered and washed with EtOAc. The filtrate and
washings were combined, dried over MgSO4, and concen-
trated to dryness. The residue was purified by silica gel
column chromatography with hexane–EtOAc (5:1–1:1) to
give 5 (11.2 g, 74%), which contained ca. 8% saturated
alcohol. This was used for the next step without further
purification. 1H NMR (270 MHz): d 3.86 (s, 6H), 6.67–6.81
(m, 3H); 13C NMR (75 MHz): d 14.71 (septet, J¼19.2 Hz),
44.41 (quintet, J¼20.0 Hz), 55.41, 55.47, 57.93 (quintet,
J¼20.9 Hz), 110.77, 111.78, 120.54, 124.41 (t, J¼25.4 Hz),
131.68, 137.91, 147.00, 148.38; IR (CHCl3): 1644, 2102,
2200, 3410 cm21. Anal. calcd for C13H10 2H8O3: C, 67.78;
147.30, 148.10; IR (CHCl3): 2110, 2225, 3350 cm21
.
2
Anal. calcd for C13H112H9O4: C, 62.61; Hþ H, 8.08.
2
Found: C, 62.73; Hþ H, 8.20.
3.1.6. (S)-1,3-Diacetoxy-5-(3,4-dimethoxyphenyl)-3-[2H3]-
methyl-[1,1,2,2,4,4-2H6]pentane (8). To a solution of 7
(6.73 g, 26.9 mmol) and DMAP (856 mg, 7.0 mmol) in
CH2Cl2 (65 ml), Et3N (10.5 ml, 75.3 mmol) was added. Then,
acetic anhydride (16.8 ml, 178 mmol) was added at 08C. The
mixture was stirred for 44 h at room temperature. Water was
added and the mixture was extracted with CH2Cl2. The
organic layer was washed with NaHCO3 aq and brine, dried
over MgSO4, filtered, and concentrated to dryness. The
residue was purified by silica gel column chromatography
with hexane–EtOAc (5:1–3:1) to give 8 (8.88 g, 99%) as an
2
2
Hþ H, 7.87. Found: C, 67.54; Hþ H, 8.11.
3.1.4. (2S,3S)-2,3-Epoxy-5-(3,4-dimethoxyphenyl)-3-
[2H3]methyl-[1,1,2,2,4,4-2H5]pentan-1-ol (6). Titanium
tetraisopropoxide (9.4 ml, 31.8 mmol, 110 mol%) and (L)-
(þ)-diisopropyl tartrate (6.67 ml, 31.7 mmol, 110 mol%)
were added to a mixture of powdered molecular sieves 4A
(14 g) in CH2Cl2 (152 ml) at 2258C, and the mixture was
stirred for 30 min at the same temperature. A solution of 5
(6.70 g, 29.1 mmol) in CH2Cl2 (90 ml) was added dropwise,
1
oil. [a]2D6¼21.32 (c 0.90, CHCl3); H NMR (300 MHz): d
2.00 (s, 3H), 2.05 (s, 3H), 3.87 (s, 6H, 6.69–6.82 (m, 3H); 13
C
NMR (75 MHz): d 20.67, 22.16, 22.63 (septet, J¼20.4 Hz),
35.34 (quintet, J¼18.7 Hz), 42.97 (quintet, J¼18.2 Hz),
55.48, 59.55 (quintet, J¼21.6 Hz), 82.20, 110.53, 113.34,
122.36, 128.60, 147.48, 148.12, 170.22, 170.65; IR (CHCl3):
1728, 2386, 3658 cm21. Anal. calcd for C17H152H9O6: C,
t
followed by a solution of BuOOH (5–6 M solution in
decane, 11.6 ml). The mixture was stirred at 2258C for 1 h.
An aqueous 10% tartaric acid solution (66 ml) was added,
and the matter was filtered and washed with CH2Cl2. The
organic layer was separated and the aqueous phase was
extracted with CH2Cl2, The combined organic layer was
washed with brine, dried over MgSO4, and concentrated to
dryness. The residue was dissolved in ether (166 ml), and
1N NaOH aq (55 ml) was added at 08C. The mixture was
stirred at 08C for 30 min and the organic layer was
separated. The aqueous phase was extracted with ether.
The combined organic layer was washed with brine, dried
over MgSO4, filtered, and concentrated to dryness. The
residue was purified by silica gel column chromatography
with hexane–EtOAc (5:1–1:1) to give 6 (6.39 g) as
colorless solid. Recrystallization of the solid from EtOAc
gave crystalline 6 (5.48 g, 77%). Mp 79.9–81.18C;
[a]2D6¼28.44 (c 1.00, CHCl3); 1H NMR (270 MHz): d
3.87 (s, 3H), 3.88 (s, 3H), 6.72–6.82 (m, 3H); 13C NMR
(75 MHz): d 15.56 (septet, J¼19.3 Hz), 41.83 (quintet,
J¼18.9 Hz), 55.52, 60.20 (quintet, J¼22.2 Hz), 60.56,
61.28 (t, J¼25.4 Hz), 109.73, 112.31, 121.25, 128.90,
2
2
61.23; Hþ H, 7.26. Found: C, 61.34; Hþ H, 7.32.
3.1.7. (R)-3,5-Diacetoxy-3-[2H3]methyl-[1,1,2,2,4,4-2H6]-
pentanoic acid (9). To
a mixture of 8 (8.35 g,
25.0 mmol) and NaIO4 (96.8 g, 45.3 mmol) in CCl4
(57 ml), CH3CN (57 ml), and phosphate buffer (90 ml,
pH¼7), RuCl3·nH2O (171 mg) was added at 08C. The
mixture was stirred below 208C for 1 h, and then ether
(50 ml) was added. The mixture was filtered through a pad
of celite and the residue was washed with CH2Cl2. The
organic layer of the filtrate and washings were combined,
and concentrated to dryness. The residue was purified by
silica gel column chromatography with CHCl3–MeOH
(50:1–10:1) to give 9 (4.26 g, 71%) as an oil. [a]2D6¼22.8
(c 0.97, ethanol); 1H NMR (300 MHz): d 2.01 (s, 3H), 2.05
(s, 3H); 13C NMR (75 MHz): d 20.78, 22.01, 23.28 (septet,
J¼19.1 Hz), 35.93 (quintet, J¼19.7 Hz), 41.93 (quintet,
J¼19.3 Hz), 59.42 (quintet, J¼21.7 Hz), 79.40, 170.53,
171.09, 175.21; IR (CHCl3): 1732, 2131, 2243, 2364, 2672,
3435, 3467, 3502, 3587, 3670 cm21. Anal. calcd for C10H7
147.45, 148.42; IR (CHCl3): 2105, 2223, 3450 cm21
.
2
2
2
Anal. calcd for C13H10 2H8O4: C, 63.37; Hþ H, 7.36.
2H9O6: C, 49.77; Hþ H, 6.68. Found: C, 47.53; Hþ H,
2
Found: C, 63.56; Hþ H, 7.47.
6.75.

6038
T. Eguchi et al. / Tetrahedron 59 (2003) 6035–6038
Santaniello, E. J. Chem. Soc., Perkin Trans. 1 1987, 2301.
(e) Rousseau, B.; Beaucourt, J. P.; Pichat, L. J. Labelled
Compd. Radiopharm. 1983, 20, 537. (f) Tanabe, M.; Peters,
R. H. Org. Synth. 1981, 60, 92. (g) Lawson, J. A.; Colwell,
W. T.; DeGraw, J. I.; Peters, R. H.; Dehn, R. L.; Tanabe, M.
Synthesis 1975, 729. (h) Scott, A. I.; Phillips, G. T.; Reichardt,
P. B.; Sweeny, J. G. J. Chem. Soc., Chem. Commun. 1970,
1396. (i) Pichat, L.; Blagoev, B.; Hardouin, J. C. Bull. Soc.
Chim. Fr. 1968, 4489. (j) Matsuo, M.; Kasida, Y. J. Labelled
Compd. 1968, 4, 134.
3.1.8. (R)-Mevalonolactone-d9 (1). To a solution of 9
(3.64 g, 15.0 mmol) in methanol (58 ml), K2CO3 (3.52 g,
25.0 mmol) was added. The mixture was stirred at room
temperature for 2.5 h. 2 M HCl was added to make pH 7,
and methanol was evaporated in vacuo. Then, 2 M HCl was
added again to pH 2. The mixture was stirred at room
temperature for 10 h. The resulting solution was extracted
several times with CHCl3. The combined organic layer was
washed with brine, dried over Na2SO4, filtered, and
concentrated to dryness. The residue was purified by silica
gel column chromatography with ether to give 1 (1.79 g,
5. (a) Krohn, K.; Meyer, A. Liebigs Ann. Chem. 1994, 167. (b)
Ohta, T.; Tabei, N.; Nozoe, S. Heterocycles 1989, 28, 425. (c)
Zamir, L. O.; Nguyen Cong, D. J. Labelled Compd. Radio-
pharm. 1988, 25, 1189. (d) Schneider, J. A.; Yoshihara, K.
J. Org. Chem. 1986, 51, 1077. (e) Phillips, G. T.; Clifford,
K. H. Eur. J. Biochem. 1976, 61, 271. (f) Cornforth, J. W.;
Ross, F. P.; Wakselman, C. J. Chem. Soc., Perkin Trans. 1
1975, 429.
1
86%) as an oil. [a]2D1¼220.5 (c 6.13, ethanol); H NMR
(300 MHz): d 1.9 (br, 1H); 13C NMR (100 MHz): d 28.47
(septet, J¼19.1 Hz), 34.63 (quintet, J¼19.3 Hz), 43.81
(quintet, J¼19.4 Hz), 65.65 (quintet, J¼23.0 Hz), 67.50,
2
2
171.59; H NMR (61 MHz, CHCl3): d 4.59 (1£ H), 4.30
2
2
2
2
(1£ H), 2.60 (1£ H), 2.48 (1£ H), 1.82 (2£ H), 1.30
2
(3£ H); IR (CHCl3): 1716, 2121, 2227, 3434, 3600,
2
2
3670 cm21. Anal. calcd for C6H1 H9O3: C, 51.76; Hþ H,
6. Kishida, M.; Yamauchi, N.; Sawada, K.; Ohashi, Y.; Eguchi,
T.; Kakinuma, K. J. Chem. Soc., Perkin Trans. 1 1997, 891.
7. Eguchi, T.; Morita, M.; Kakinuma, K. J. Am. Chem. Soc. 1998,
120, 5427.
2
7.24. Found: C, 51.51; Hþ H, 7.51.
Acknowledgements
8. (a) Eguchi, T.; Takyo, H.; Morita, M.; Kakinuma, K.; Koga, Y.
Chem. Commun. 2000, 1545. (b) Kakinuma, K.; Dekishima,
Y.; Matsushima, Y.; Eguchi, T.; Misawa, N.; Takagi, M.;
Kuzuyama, T.; Seto, H. J. Am. Chem. Soc. 2001, 123, 1238. (c)
Eguchi, T.; Dekishima, Y.; Hamano, Y.; Dairi, T.; Seto, H.;
Kakinuma, K. J. Org. Chem. 2003, 68, 5433.
This work was partially supported by Grant-in-Aid for
Scientific Research from the Ministry of Education, Culture,
Science, Sports, and Technology, Japan.
9. (a) Goerger, M. M.; Hudson, B. S. J. Org. Chem. 1988, 53,
3148. (b) Gerlach, H. Helv. Chim. Acta 1966, 48, 1291.
10. (a) Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980, 102,
5974. (b) Gai, Y.; Robert, M. H.; Klunder, J. M.; Ko, S. Y.;
Masamune, H.; Sharpless, K. B. J. Am. Chem. Soc. 1987, 109,
5765.
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