Abstract
Alkyne carboxylic acid derivatives are stable, non-toxic, inexpensive, and commercially available. They are prevalent intermediates for various synthetic transformations. In recent years, decarboxylative oxidative alkynylation reactions involving direct C−H bond activation of diverse carbo- and hetero-cycles with alkyne carboxylic acid have attracted more and more interest from the synthetic community. The joy and challenges of direct oxidative decarboxylative alkynylation have been discussed in detail to enlighten this highly emerging area. More emphasis is being placed on the fascinating implementation and advancement of various methods for the formation of C(SP2)-C(SP) bonds. This short review mainly focuses on developments of the decarboxylative oxidative alkynylation reaction, considering the uniqueness of each protocol by highlighting the substrate scope, selectivity, and yields in conjunction with mechanistic insights.
Keywords: Oxidative coupling, decarboxylative reaction, C–H alkynylation, alkynes, heterocycles, C(SP2)- C(SP) bond.
Graphical Abstract
[http://dx.doi.org/10.1002/anie.200602761] [PMID: 17335070]
[http://dx.doi.org/10.1039/c1cs15071e] [PMID: 21655588]
[http://dx.doi.org/10.1021/cr050992x] [PMID: 17305399]
[http://dx.doi.org/10.1002/anie.200802270] [PMID: 18683173]
[http://dx.doi.org/10.1021/cr030009u] [PMID: 16092827]
[http://dx.doi.org/10.1016/j.tet.2009.06.028]
[http://dx.doi.org/10.1016/j.tetlet.2019.151415]
[http://dx.doi.org/10.1039/c1cs15093f] [PMID: 21792454]
[http://dx.doi.org/10.1002/anie.201705107]
[http://dx.doi.org/10.1021/acs.chemrev.6b00516] [PMID: 28266216]
[http://dx.doi.org/10.1021/acs.joc.8b01080] [PMID: 29986581]
[http://dx.doi.org/10.1016/S0040-4039(00)91094-3]
[http://dx.doi.org/10.1002/anie.200801539] [PMID: 18506862]
[http://dx.doi.org/10.1002/chem.200802444] [PMID: 19123225]
[http://dx.doi.org/10.1021/jo902015w] [PMID: 19860393]
[http://dx.doi.org/10.1021/ja038177r] [PMID: 14599185]
[http://dx.doi.org/10.1021/jo051882t] [PMID: 16388664]
[http://dx.doi.org/10.1002/anie.200353015] [PMID: 14679552]
[http://dx.doi.org/10.1021/jo100460v] [PMID: 20420397]
[http://dx.doi.org/10.1021/ol703130y] [PMID: 18229935]
[http://dx.doi.org/10.1039/c2cs35034c] [PMID: 22513709]
[http://dx.doi.org/10.1002/cssc.200700004] [PMID: 18605670]
[http://dx.doi.org/10.1016/j.tetlet.2009.11.003]
[http://dx.doi.org/10.1039/c001277g] [PMID: 20361097]
[http://dx.doi.org/10.1055/s-0032-1318119]
[http://dx.doi.org/10.24820/ark.5550190.p011.559]
[http://dx.doi.org/10.1002/anie.200906755] [PMID: 20191647]
[http://dx.doi.org/10.1021/ja026108r] [PMID: 12121084]
[http://dx.doi.org/10.1021/ol901684h] [PMID: 19739688]
[http://dx.doi.org/10.1021/jo9025622] [PMID: 20073529]
[http://dx.doi.org/10.1021/ol901049r] [PMID: 19555067]
[http://dx.doi.org/10.1021/ja072718l] [PMID: 17539646]
[http://dx.doi.org/10.1002/anie.200904776] [PMID: 19902446]
[http://dx.doi.org/10.1021/ol100488v] [PMID: 20337427]
[http://dx.doi.org/10.1002/anie.201003179] [PMID: 20730846]
[http://dx.doi.org/10.1002/anie.200905419] [PMID: 19894245]
[http://dx.doi.org/10.1002/chem.201200200] [PMID: 22438043]
[http://dx.doi.org/10.1021/ol203289v] [PMID: 22260441]
[http://dx.doi.org/10.1021/acs.accounts.7b00148] [PMID: 28636313]
[http://dx.doi.org/10.1016/j.jorganchem.2012.11.029]
[http://dx.doi.org/10.1016/j.jorganchem.2017.04.025]
[http://dx.doi.org/10.1002/adsc.201200876]
[http://dx.doi.org/10.1021/jo400574d] [PMID: 23573947]
[http://dx.doi.org/10.1039/C3RA47712F]
[http://dx.doi.org/10.1039/C6RA12916A]
[http://dx.doi.org/10.1021/jo802290r] [PMID: 19099411]
[http://dx.doi.org/10.1021/jo1010284] [PMID: 20578679]
[http://dx.doi.org/10.1002/ejoc.201101770]
[http://dx.doi.org/10.1021/jo101398a] [PMID: 20795634]
[http://dx.doi.org/10.1016/j.tetlet.2010.11.110]
[http://dx.doi.org/10.1016/j.tetlet.2011.07.091]
[http://dx.doi.org/10.1016/j.tetlet.2017.02.073]
[http://dx.doi.org/10.1016/j.tet.2012.06.003]
[http://dx.doi.org/10.1016/j.catcom.2017.05.025]
[http://dx.doi.org/10.1039/c0cc03772a] [PMID: 21049135]
[http://dx.doi.org/10.1039/c1ob05969f] [PMID: 21904730]
[http://dx.doi.org/10.1039/C6RA23742H]
[http://dx.doi.org/10.1002/adsc.201300561]
[http://dx.doi.org/10.1002/slct.201600113]
[http://dx.doi.org/10.1002/adsc.201100238]
[http://dx.doi.org/10.1021/acs.joc.7b02175] [PMID: 28965408]
[http://dx.doi.org/10.1021/acsomega.7b01165] [PMID: 31457871]
[http://dx.doi.org/10.1016/j.tetlet.2015.02.029]
[http://dx.doi.org/10.1039/C7NJ00877E]
[http://dx.doi.org/10.1016/j.tet.2014.05.087]
[http://dx.doi.org/10.1016/j.tetlet.2016.09.054]
[http://dx.doi.org/10.1039/c0cc00403k] [PMID: 20490417]
[http://dx.doi.org/10.1016/j.tetlet.2016.08.095]
[http://dx.doi.org/10.1021/acs.joc.5b02361] [PMID: 26618610]
[http://dx.doi.org/10.1016/j.catcom.2017.10.018]
[http://dx.doi.org/10.1039/c3cs60041f] [PMID: 23467811]
[http://dx.doi.org/10.1016/j.tetlet.2016.12.058]
[http://dx.doi.org/10.1039/C8NJ02964D]
[http://dx.doi.org/10.1021/cr500431s] [PMID: 26558751]
[http://dx.doi.org/10.1021/acs.chemrev.9b00045] [PMID: 31074264]
[http://dx.doi.org/10.1021/acs.chemrev.8b00507] [PMID: 30480438]
[http://dx.doi.org/10.1021/acs.chemrev.6b00567] [PMID: 28085272]
[http://dx.doi.org/10.1016/j.ccr.2017.04.012]
[http://dx.doi.org/10.1039/C6CS00075D] [PMID: 27072661]
[http://dx.doi.org/10.1016/j.ccr.2017.06.018]
[http://dx.doi.org/10.1039/C7CS00619E] [PMID: 29911724]
[http://dx.doi.org/10.1039/C8CS00872H] [PMID: 31282495]
[http://dx.doi.org/10.1002/asia.201800102] [PMID: 29575823]
[http://dx.doi.org/10.1002/ajoc.201900733]
[http://dx.doi.org/10.1021/jo102175f] [PMID: 21222475]
[http://dx.doi.org/10.1039/c2ob25643f] [PMID: 22868382]
[http://dx.doi.org/10.1021/acs.organomet.6b00437]
[http://dx.doi.org/10.1002/ejoc.201301441]
[http://dx.doi.org/10.1021/ja027523m] [PMID: 12236722]
[http://dx.doi.org/10.1021/ja052099l] [PMID: 16028944]
[http://dx.doi.org/10.1126/science.1128684] [PMID: 16888137]
[http://dx.doi.org/10.1021/ja068993+] [PMID: 17375927]
[http://dx.doi.org/10.1021/ol070749f] [PMID: 17542594]
[http://dx.doi.org/10.1002/anie.200905953] [PMID: 20041463]
[http://dx.doi.org/10.1021/ol100296b] [PMID: 20201587]
[http://dx.doi.org/10.1021/ja910461e] [PMID: 20131777]
[http://dx.doi.org/10.1002/adsc.200900502]
[http://dx.doi.org/10.1016/j.tet.2015.02.020]
[http://dx.doi.org/10.1055/s-0036-1588115]
[http://dx.doi.org/10.1002/slct.201800758]
[http://dx.doi.org/10.1021/ja304539j] [PMID: 22681310]
[http://dx.doi.org/10.1002/1521-3773(20020816)41:16<2991:AID-ANIE2991>3.0.CO;2-6] [PMID: 12203435]
[http://dx.doi.org/10.1002/adsc.201701469]