1428
D. S. Matteson
material 1. The analytical sample was recrystallized twice from
methylcyclohexane and dried under vacuum, mp 82–848C.
dH (400MHz, CDCl3) 0.85 (s, 3H), 1.16 (d, J 11, 1H), 1.30(s, 3H),
1.32 (br s, position varies slightly in different spectra, 1H), 1.43
(s, 3H), 1.9 (m, 2H), 2.07 (t, J6, 1H), 2.2–2.4(m, 2H), 3.61(s, 2H),
4.35 (dd, J 2, 9, 1H). dC (100 MHz, CDCl3) 24.0, 26.4, 27.0, 28.5,
35.2, 38.1, 39.4, 49.7 (broad, ,150 Hz at half-height), 51.1, 78.4,
86.7. m/z (HR) (C11H19BO3 þ Naþ) calcd. 233.1321, found
233.1340. Anal. Calc. for C11H19BO3: C 62.89, H 9.12, B 5.15.
Found: C 62.45, 62.20, H 9.93, 10.43, B 4.73, 4.79%.
Reaction of Pinanediol (Bromomethyl)boronate with
Sodium Hydroxide. Pinanediol (bromomethyl)boronate[3c]
(12 mg) in D2O (,1 mL) with sodium hydroxide (1 M in D2O,
1
0.16 mL) formed a gross mixture of products. The H NMR
spectrum taken after 0.7 h showed a major proportion of
unchanged bromomethyl compound and its hydroxylated anions
at d 2.24 (s), 2.25, (s) 2.27 (s), 3.79 (dd, J 3, 8), 3.91 (dd, J 2, 8),
with ,30 % conversion to a mixture of hydroxymethyl deriva-
tives at d 2.5–2.9. After 2 h at 20–258C, the reaction appeared to
be ,70 % complete, and after several days 100 % complete.
dH (300 MHz, D2O) 0.66–2.3 (overlapping patterns typical of
pinanediol boronic esters), 2.41 (d, J 13), 2.59 (d, J 13), 2.66 (s).
2.68 (s), 2.73 (s), 2.83 (d, J 13), 2.89 (d, J 13), 3.39 (dd, J 3, 9),
3.72 (dd, J 3, 9), 3.88 (dd, J 2, 8). Relative peak heights indicated
pairing of the doublet at d 2.41 with one of the doublets at d 2.83
or 2.89, and at d 2.59 with the other doublet at d 2.89 or 2.83.
Integral values appeared to favour the first alternative in each
case but were not accurate enough for definite assignment. The
singlet at d 2.73 was consistently twice as high as that at d 2.68,
and the singlet at d 2.66 grew to be slightly larger than that at
d 2.68 at the conclusion of the reaction. The group of singlets had
an integral approximately equal to the sum of the doublets. The
double doublets at d 3.39 and 3.72 had integrals corresponding
to the doublets in the 2.4–2.9 region, that at d 3.88 with the
2.73 singlet, and that at d 3.72 with the 2.68 singlet, leaving the
d 2.66 singlet unaccounted for, possibly paired with an obscured
double doublet. No DCH2OD was detected.
Decomposition of 2,5-dihydroxy-1,4,2,5-dioxadiborinane
(11) buffered at pH ,7. A solution of 11 (44 mg, 0.38 mmol) in
D2O (0.7 mL) was prepared: dH (400 MHz) 1.99 (s, 0.03H,
impurity), 3.20 (s, 2H, B-CH2); 4.62 (s, 1.73 H, HOD);
dC (100 MHz) 30.1 (sharp, about the same height as the major
peak), 50.2 (width 160 Hz at half-height, C-B). Sodium hydrox-
ide in D2O (0.1 mL, ,1 M) was added: dH 2.01 (s, 0.03H,
impurity); 3.13 (s, 2H, BCH2), 4.61 (s, 1.9H), 5.27 (s, impurity);
dC (100 MHz) 51.1 (width ,400 Hz at half-height), 30.1 (impu-
rity), 81.6 (impurity). The NMR tube was heated in a water bath
at 90–968C ,1.5 h: dH (400 MHz) 3.12 (t, JHD 1.6, CDH2),
3.14 (s, CH3), 3.15 (width ,90 Hz at half-height, BCH2) (total
near d 3, 1.4H), 4.60 (1.9H, HOD); dC (100 MHz) 24.3 (impurity),
48.47 (t, JCD 22), 48.74, 49.9 (,200 Hz wide at half-height),
63 (,600 Hz wide at half-height), 67.2 (,200 Hz wide at half-
height), 81.6 (impurity). Spectra taken after an additional 2 h and
then 2.5 h heating at 90–978C showed similar DCH2OH/CH3OH
1
peaks and increasingly broad and indistinct H and 13C reso-
Accessory Publication
nances attributed to HOCH2B units, while the 1H integral ratio
of CH to OH fell from the original 1.05 to 0.47. There were
minor changes in impurity peaks, including an increase in the
13C absorption at d 81.6. Finally, methanol (3 mL) was added and
found to coincide with the 1H signal at d 3.19 and the 13C signal
at d 48.72. The DEPT spectrum confirmed that the triplet at d
48.45 was owing to a CH2 group, that at 48.72 was CH3, and the
impurity peak at 81.6 was a CH2 group.
1H NMR and 13C NMR spectra of 12 and of the degradation of
11 with base are available as an accessory publication on the
Journal’s website.
Acknowledgment
I thank the William H. Prusoff Foundation for a gift in support of this work.
The WSU NMR Center equipment was supported by NIH grants
RR0631401 and RR12948, NSF grants CHE-9115282 and DBI-9604689
and the Murdock Charitable Trust.
Stability Studies on Pinanediol (Hydroxymethyl)boronate
(12). Pinanediol ester 12 (7 mg) dissolved completely in
D2O (1 mL) after addition of sodium hydroxide (0.06 mL of
1 M), resulting pH $ 11: dH (300 MHz, D2O) 0.66–2.3 (pinane-
diol pattern with extra peaks), 2.66, 2.68, 2.72 (s, s, s, ratio
,1:2:4, 2H), 3.77 (dd, J 3, 9, 0.3H), 3.88 (dd, J 2, 8, 0.6H),
3.9 (m, partially obscured, 0.1H), 4.65 (s, HOD). No change was
observed after 20 h at 22–238C. Addition of methanol (5 mL)
introduced a sharp singlet, d 3.16 (integral 1.4ꢁ, peak height
5.7ꢁ that at d 2.72). A second sample of 12 (8 mg) in D2O
(1 mL) and 1M sodium hydroxide in D2O (0.2 mL) was heated
for 3 h at 90–978C: dH 0.64–2.1 (pinanediol pattern with extra
peaks, 15H), 2.65, 2.67, 2.72 (s, s, s, ratio 3:1:2, 0.7H total),
3.13 (t, JDH 3, 0.6H), 3.15 (s, 0.02H), 3.7–3.9 (m, 1H), 4.65
(s, HOD, 7.9H). The estimated HOD concentration is 0.25–0.3 M.
The solubility of 12 in neutral or acidic D2O is low,
,3 mg mLꢀ1. A solution acidified with a small drop of acetyl
chloride showed evidence of 40 % dissociation to pinanediol
and free (hydroxymethyl)boronic acid (10) or its dimer (11): for
12 dH (400 MHz) 3.29 (d, J 17), 3.31 (d, J 17), 4.29 (dd, J 2, 9);
for 10/11 dH (400 MHz) 3.18 (s); free pinanediol, 3.88 (dd, J 6,
10), integral ratios for 12/10, 59/41. A pure sample of pinanediol
in D2O had a similar signal at d 3.91 (dd, J 6, 10). In D2O with
sodium bicarbonate, the free pinanediol resonated at d 3.90,
similar couplings, while 12 had broadened, unresolved multi-
plets at d 3.75 and 4.21, broad singlet at 3.20, and 10/11 had a
less broad singlet at 3.17.
References
[1] D. S. Matteson, M. L. Peterson, J. Org. Chem. 1987, 52, 5116.
doi:10.1021/JO00232A011
[2] D. S. Matteson, A. A. Kandil, R. Soundararajan, J. Am. Chem. Soc.
1990, 112, 3964. doi:10.1021/JA00166A037
[3] (a) D. S. Matteson, A. A. Kandil, J. Org. Chem. 1987, 52, 5121.
doi:10.1021/JO00232A012
(b) O. C. Ho, R. Soundararajan, J. Lu, D. S. Matteson, Z. Wang,
X. Chen, M. Wei, R. D. Willett, Organometallics 1995, 14, 2855.
doi:10.1021/OM00006A034
(c) D. S. Matteson, R. Soundararajan, O. C. Ho, W. Gatzweiler,
Organometallics 1996, 15, 152. doi:10.1021/OM950574Q
(d) D. S. Matteson, J.-J. Yang, Tetrahedron Asymmetry 1997, 8,
3855. doi:10.1016/S0957-4166(97)00569-7
(e) D. S. Matteson, J. Lu, Tetrahedron Asymmetry 1998, 9, 2423.
doi:10.1016/S0957-4166(98)00233-X
[4] R. P. Singh, D. S. Matteson, J. Org. Chem. 2000, 65, 6650.
doi:10.1021/JO005522B
[5] D. S. Matteson, R. W. H. Mah, J. Am. Chem. Soc. 1963, 85,
2599. doi:10.1021/JA00900A017
[6] K. M. Sadhu, D. S. Matteson, Organometallics 1985, 4, 1687.
doi:10.1021/OM00128A038
[7] T. J. Michnick, D. S. Matteson, Synlett 1991, 631. doi:10.1055/S-1991-
20821
[8] (a) D. S. Matteson, T. C. Cheng, J. Organomet. Chem. 1966, 6, 100.
doi:10.1016/S0022-328X(00)83357-4
(b) D. S. Matteson, T.-C. Cheng, J. Org. Chem. 1968, 33, 3055.
doi:10.1021/JO01272A008