Theor Chem Acc (2016) 135:13
1 3
good agreement with experimental
11 B chemical shifts;
thus, computational methods can unveil detailed mechanistic hydroboration pathways and accurately predict the
NMR peaks of specifi c products, verifying the reaction
mechanism.
Studying the experimental conditions necessary to
secure a specifi c product would prove to be an interesting
avenue of research to pursue, as current procedures allow
for the possibility of multiple product species, such as
dimers, polymers, and oligomeric species. Quantum chemical calculations thus lend themselves as useful tools to help
design novel enantio- and diastereoselective chemical synthesis strategies. They are also becoming easily available
standard tools that are accessible in undergraduate education for computational laboratories.
Acknowledgments LH was supported by the King’s Undergraduate Research Fellowships. ER gratefully acknowledges Péter Surján
and the inspiration she received from the undergraduate research in
his laboratory, leading to her fi rst papers. Péter continues to inspire
her work through research and teaching, including this study that was
carried out together with undergraduate students at King’s College,
London.
Open Access This article is distributed under the terms of the
Creative Commons Attribution 4.0 International License ( http://creativecommons.org/licenses/by/4.0/ ), which permits unrestricted use,
distribution, and reproduction in any medium, provided you give
appropriate credit to the original author(s) and the source, provide a
link to the Creative Commons license, and indicate if changes were
made.
References
1. Yang DT, Mellerup SK, Wang X, Lu JS, Wang SN (2015)
Reversible 1,1-hydroboration: boryl Insertion into a C–N Bond
and competitive elimination of HBR2 or R–H. Angew Chem Int
Ed 54(18):5498–5501. doi: 10.1002/anie.201500487
2. Fan XT, Zheng JH, Li ZH, Wang HD (2015) Organoborane catalyzed regioselective 1,4-hydroboration of pyridines. J Am Chem
Soc 137(15):4916–4919. doi: 10.1021/jacs.5b03147
3. Chong CC, Hirao H, Kinjo R (2015) Metal-free sigma-bond
metathesis in 1,3,2-diazaphospholene-catalyzed hydroboration
of carbonyl compounds. Angew Chem Int Ed 54(1):190–194.
doi: 10.1002/anie.201408760
4. Taniguchi T, Curran DP (2014) Hydroboration of arynes
with N-heterocyclic carbene boranes. Angew Chem Int Ed
53(48):13150–13154. doi: 10.1002/anie.201408345
5. Sztáray B, Rosta E, Böcskey Z, Szepes L (1999) Geometry and electronic structure of bis(tetrahydridoborato)
bis(cyclopentadienyl)zirconium(IV). J Organomet Chem
582(2):267–272. doi: 10.1016/S0022-328X(99)00062-5
6. Suzuki A (2010) Organoboranes in organic synthesis including
suzuki coupling reactions. Jpn Inst Heterocycl Chem 80(1):15–
43. doi: 10.3987/COM-09-S(S)Summary
7. Allais C, Tsai AS, Nuhant P, Roush WR (2013) Highly diastereo- and enantioselective aldol reactions of stereochemically
defi ned tetrasubstituted enolborinates generated by 1,4-hydroboration of α, β-unsaturated morpholine carboxamides
with (diisopinocampheyl)borane. Angew Chem Int Ed Engl
52(49):12888–12891. doi: 10.1002/anie.201307302
8. Dhillon RS (2007) Hydroboration and organic synthesis: 9-borabicyclo[3.3.1]nonane (9-BBN). doi: 10.1007/978-3-540-49076-0
9. Hu NF, Zhao GQ, Zhang YY, Liu XQ, Li GY, Tang WJ (2015)
Synthesis of chiral alpha-amino tertiary boronic esters by enantioselective hydroboration of alpha-arylenamides. J Am Chem Soc
137(21):6746–6749. doi: 10.1021/jacs.5b03760
10. Obligacion JV, Neely JM, Yazdani AN, Pappas I, Chirik PJ
(2015) Cobalt catalyzed Z-selective hydroboration of terminal
alkynes and elucidation of the origin of selectivity. J Am Chem
Soc 137(18):5855–5858. doi: 10.1021/jacs.5b00936
11. Zhang L, Zuo ZQ, Wan XL, Huang Z (2014) Cobalt-catalyzed
enantioselective hydroboration of 1,1-disubstituted aryl alkenes.
J Am Chem Soc 136(44):15501–15504. doi: 10.1021/ja5093908
12. Klotter F, Studer A (2015) Short and divergent total synthesis of (+)-machaeriol B, (+)-machaeriol D, (+)-delta(8)-THC,
and analogues. Angew Chem Int Ed Engl 54(29):8547–8550.
doi: 10.1002/anie.201502595
13. Yang Y, Xu M, Song D (2015) Organocatalysts with carbon-centered activity for CO 2 reduction with boranes. Chem Commun
(Camb UK) 51(56):11293–11296. doi: 10.1039/c5cc04337a
14. Niu H, Dong J-Y (2015) Regio-chemistry control in propylene/
isoprene copolymerization by metallocene catalysts. Polym Int
64(8):1023–1029. doi: 10.1002/pi.4878
15. Brown HC, Negishi EI, Burke PL (1971) Organoboranes. 12.
Hydroboration of 1,3-butadiene with borane in tetrahydrofuran
in a ratio equal to or smaller than 1 1—interconversion between
B-alkylborolanes and 1,2-tetramethylenediboranes. J Am Chem
Soc 93(14):3400. doi: 10.1021/ja00743a017
16. Brown HC, Negishi EI, Gupta SK (1970) Reaction of B-methoxydialkylboranes with lithium aluminum hydride in presence
of olefi ns—a new and general synthesis of acyclic and cyclic
mixed trialkylboranes and their conversion into corresponding
trialkylcarbinols via carbonylation–oxidation. J Am Chem Soc
92(22):6648. doi: 10.1021/ja00725a050
17. Andreou A, Leskes M, Jambrina PG, Tustin GJ, Grey CP, Rosta
E, Scherman OA (2015) Divergence from the classical hydroboration reactivity; boron containing materials through a hydroboration cascade of small cyclic dienes. Chem Sci. doi: 10.1039/
C4SC02729A
18. Brown HC, Bhat KS (1986) Hydroboration 76. Hydroboration
of cyclic dienes with representative hydroborating agents. J Org
Chem 51(4):445–449. doi: 10.1021/jo00354a005
19. Zweifel G, Nagase K, Brown HC (1962) Hydroboration. XIII.
The hydroboration of dienes with disiamylborane. A convenient
procedure for the conversion of selected dienes into unsaturated
alcohols. J Am Chem Soc 84(2):190–195
20. Zweifel G, Nagase K, Brown HC (1962) Hydroboration. XII.
The hydroboration of dienes with diborane. J Am Chem Soc
84(2):183–189. doi: 10.1021/ja00861a012
21. Houk KN, Rondan NG, Wu Y-D, Metz JT, PaddonRow MN (1984) Theoretical studies of stereoselective
hydroborations.
Tetrahedron
40(12):2257–2274.
doi: 10.1016/0040-4020(84)80009-5
22. Ess DH, Kister J, Chen M, Roush WR (2009) Quantum-mechanical study of 10-R-9-borabicyclo[3.3.2]decane alkene hydroboration. J Org Chem 74(22):8626–8637. doi: 10.1021/jo901737d
23. Ilich P-P, Rickertsen LS, Becker E (2006) Polar addition to
C=C group: why is anti-Markovnikov hydroboration–oxidation
of alkenes not “anti-”? J Chem Educ 83(11):1681. doi: 10.1021/
ed083p1681
24. Oyola Y, Singleton DA (2009) Dynamics and the failure of transition state theory in alkene hydroboration. J Am Chem Soc
131(9):3130–3131. doi: 10.1021/ja807666d
247
Reprinted from the journal
1 3
good agreement with experimental
11 B chemical shifts;
thus, computational methods can unveil detailed mechanistic hydroboration pathways and accurately predict the
NMR peaks of specifi c products, verifying the reaction
mechanism.
Studying the experimental conditions necessary to
secure a specifi c product would prove to be an interesting
avenue of research to pursue, as current procedures allow
for the possibility of multiple product species, such as
dimers, polymers, and oligomeric species. Quantum chemical calculations thus lend themselves as useful tools to help
design novel enantio- and diastereoselective chemical synthesis strategies. They are also becoming easily available
standard tools that are accessible in undergraduate education for computational laboratories.
Acknowledgments LH was supported by the King’s Undergraduate Research Fellowships. ER gratefully acknowledges Péter Surján
and the inspiration she received from the undergraduate research in
his laboratory, leading to her fi rst papers. Péter continues to inspire
her work through research and teaching, including this study that was
carried out together with undergraduate students at King’s College,
London.
Open Access This article is distributed under the terms of the
Creative Commons Attribution 4.0 International License ( http://creativecommons.org/licenses/by/4.0/ ), which permits unrestricted use,
distribution, and reproduction in any medium, provided you give
appropriate credit to the original author(s) and the source, provide a
link to the Creative Commons license, and indicate if changes were
made.
References
1. Yang DT, Mellerup SK, Wang X, Lu JS, Wang SN (2015)
Reversible 1,1-hydroboration: boryl Insertion into a C–N Bond
and competitive elimination of HBR2 or R–H. Angew Chem Int
Ed 54(18):5498–5501. doi: 10.1002/anie.201500487
2. Fan XT, Zheng JH, Li ZH, Wang HD (2015) Organoborane catalyzed regioselective 1,4-hydroboration of pyridines. J Am Chem
Soc 137(15):4916–4919. doi: 10.1021/jacs.5b03147
3. Chong CC, Hirao H, Kinjo R (2015) Metal-free sigma-bond
metathesis in 1,3,2-diazaphospholene-catalyzed hydroboration
of carbonyl compounds. Angew Chem Int Ed 54(1):190–194.
doi: 10.1002/anie.201408760
4. Taniguchi T, Curran DP (2014) Hydroboration of arynes
with N-heterocyclic carbene boranes. Angew Chem Int Ed
53(48):13150–13154. doi: 10.1002/anie.201408345
5. Sztáray B, Rosta E, Böcskey Z, Szepes L (1999) Geometry and electronic structure of bis(tetrahydridoborato)
bis(cyclopentadienyl)zirconium(IV). J Organomet Chem
582(2):267–272. doi: 10.1016/S0022-328X(99)00062-5
6. Suzuki A (2010) Organoboranes in organic synthesis including
suzuki coupling reactions. Jpn Inst Heterocycl Chem 80(1):15–
43. doi: 10.3987/COM-09-S(S)Summary
7. Allais C, Tsai AS, Nuhant P, Roush WR (2013) Highly diastereo- and enantioselective aldol reactions of stereochemically
defi ned tetrasubstituted enolborinates generated by 1,4-hydroboration of α, β-unsaturated morpholine carboxamides
with (diisopinocampheyl)borane. Angew Chem Int Ed Engl
52(49):12888–12891. doi: 10.1002/anie.201307302
8. Dhillon RS (2007) Hydroboration and organic synthesis: 9-borabicyclo[3.3.1]nonane (9-BBN). doi: 10.1007/978-3-540-49076-0
9. Hu NF, Zhao GQ, Zhang YY, Liu XQ, Li GY, Tang WJ (2015)
Synthesis of chiral alpha-amino tertiary boronic esters by enantioselective hydroboration of alpha-arylenamides. J Am Chem Soc
137(21):6746–6749. doi: 10.1021/jacs.5b03760
10. Obligacion JV, Neely JM, Yazdani AN, Pappas I, Chirik PJ
(2015) Cobalt catalyzed Z-selective hydroboration of terminal
alkynes and elucidation of the origin of selectivity. J Am Chem
Soc 137(18):5855–5858. doi: 10.1021/jacs.5b00936
11. Zhang L, Zuo ZQ, Wan XL, Huang Z (2014) Cobalt-catalyzed
enantioselective hydroboration of 1,1-disubstituted aryl alkenes.
J Am Chem Soc 136(44):15501–15504. doi: 10.1021/ja5093908
12. Klotter F, Studer A (2015) Short and divergent total synthesis of (+)-machaeriol B, (+)-machaeriol D, (+)-delta(8)-THC,
and analogues. Angew Chem Int Ed Engl 54(29):8547–8550.
doi: 10.1002/anie.201502595
13. Yang Y, Xu M, Song D (2015) Organocatalysts with carbon-centered activity for CO 2 reduction with boranes. Chem Commun
(Camb UK) 51(56):11293–11296. doi: 10.1039/c5cc04337a
14. Niu H, Dong J-Y (2015) Regio-chemistry control in propylene/
isoprene copolymerization by metallocene catalysts. Polym Int
64(8):1023–1029. doi: 10.1002/pi.4878
15. Brown HC, Negishi EI, Burke PL (1971) Organoboranes. 12.
Hydroboration of 1,3-butadiene with borane in tetrahydrofuran
in a ratio equal to or smaller than 1 1—interconversion between
B-alkylborolanes and 1,2-tetramethylenediboranes. J Am Chem
Soc 93(14):3400. doi: 10.1021/ja00743a017
16. Brown HC, Negishi EI, Gupta SK (1970) Reaction of B-methoxydialkylboranes with lithium aluminum hydride in presence
of olefi ns—a new and general synthesis of acyclic and cyclic
mixed trialkylboranes and their conversion into corresponding
trialkylcarbinols via carbonylation–oxidation. J Am Chem Soc
92(22):6648. doi: 10.1021/ja00725a050
17. Andreou A, Leskes M, Jambrina PG, Tustin GJ, Grey CP, Rosta
E, Scherman OA (2015) Divergence from the classical hydroboration reactivity; boron containing materials through a hydroboration cascade of small cyclic dienes. Chem Sci. doi: 10.1039/
C4SC02729A
18. Brown HC, Bhat KS (1986) Hydroboration 76. Hydroboration
of cyclic dienes with representative hydroborating agents. J Org
Chem 51(4):445–449. doi: 10.1021/jo00354a005
19. Zweifel G, Nagase K, Brown HC (1962) Hydroboration. XIII.
The hydroboration of dienes with disiamylborane. A convenient
procedure for the conversion of selected dienes into unsaturated
alcohols. J Am Chem Soc 84(2):190–195
20. Zweifel G, Nagase K, Brown HC (1962) Hydroboration. XII.
The hydroboration of dienes with diborane. J Am Chem Soc
84(2):183–189. doi: 10.1021/ja00861a012
21. Houk KN, Rondan NG, Wu Y-D, Metz JT, PaddonRow MN (1984) Theoretical studies of stereoselective
hydroborations.
Tetrahedron
40(12):2257–2274.
doi: 10.1016/0040-4020(84)80009-5
22. Ess DH, Kister J, Chen M, Roush WR (2009) Quantum-mechanical study of 10-R-9-borabicyclo[3.3.2]decane alkene hydroboration. J Org Chem 74(22):8626–8637. doi: 10.1021/jo901737d
23. Ilich P-P, Rickertsen LS, Becker E (2006) Polar addition to
C=C group: why is anti-Markovnikov hydroboration–oxidation
of alkenes not “anti-”? J Chem Educ 83(11):1681. doi: 10.1021/
ed083p1681
24. Oyola Y, Singleton DA (2009) Dynamics and the failure of transition state theory in alkene hydroboration. J Am Chem Soc
131(9):3130–3131. doi: 10.1021/ja807666d
247
Reprinted from the journal